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The behavior of most liquid and solid mixtures cannot be represented by the cubic equations of state. For this reason, it is necessary to dene another quantity, called the activity coecient, to express fugacities of components in liquid and solid mixtures. In the literature, various activity coecient models are used in phase equilibrium calculations. The purpose of this chapter is to introduce such models and to show how to evaluate the parameters appearing in these models. 8.1 PROPERTY CHANGES ON MIXING FOR AN IDEAL MIXTURE Property change on mixing per mole, e mix , is dened by Eq. (6.3-4), i.e., e mix =

k X i=1

k P

xi (i i ) e

(8.1-1)

i=1

IM

xi (IM i ) e i Hi

IM

(8.1-2)

e = Vi

and

e = Hi

(8.1-3)

indicating that volume and enthalpy changes on mixing are both zero. For an ideal mixture this is an expected result because not only are the sizes of the molecules equal to each other, but also the interactions between unlike molecules are equal to those between like molecules. To obtain an expression for the Gibbs energy change on mixing for an ideal mixture, it is IM e necessary to relate Gi to Gi . The partial molar Gibbs energy of component i in an ideal mixture is given by Gi

IM

e IM Hmix = 0

(8.1-4)

The molar Gibbs energy of pure i is expressed by Eq. (5.2-5), i.e., e Gi = i (T ) + RT ln fi 215

b = i (T ) + RT ln fiIM = i (T ) + RT ln(xi fi )

(8.1-5)

(8.1-6)

IM

Thus, the use of Eq. (8.1-7) in Eq. (8.1-2) results in e GIM = RT mix

k X i=1

e Gi = RT ln xi xi ln xi

(8.1-7)

(8.1-8)

e For a binary mixture of components 1 and 2, a representative plot of GIM versus x1 is shown mix eIM < 0. In other words, the in Figure 8.1. Since xi < 1, it follows from Eq. (8.1-8) that Gmix Gibbs energy of an ideal mixture is always less than the summation of the Gibbs energies of the unmixed pure components. Thus, upon mixing at a specied temperature and pressure, components 1 and 2 form a stable1 ideal mixture.

~ IM S mix

x1

~ IM Gmix

To obtain an expression for the entropy change on mixing for an ideal mixture, note that e IM eIM emix GIM = Hmix T Smix | {z }

0

e eIM Figure 8.1 Representative plots of GIM and Smix as a function of composition. mix

(8.1-9)

k X i=1

xi ln xi

(8.1-10)

eIM For a binary mixture of components 1 and 2, a representative plot of Smix versus x1 is also IM > 0. e shown in Figure 8.1. Mixing increases disorder and thus Smix 8.2 EXCESS PROPERTIES In the literature, it is customary to split the property change on mixing into two terms as mix = IM + ex mix where ex is called the excess property. The use of Eq. (8.2-1) in Eq. (6.3-2) leads to mix =

k X

(8.2-1)

In other words, components 1 and 2 are completely miscible in each other. Miscibility of components will be discussed in Chapter 11 in detail.

i=1

ni i + IM + ex e mix

IM mix

(8.2-2)

{z

216

Thus, an excess property is the dierence between the actual property and the property for an ideal mixture at the same temperature, pressure, and composition of the mixture, i.e., ex (T, P, xi ) = mix (T, P, xi ) IM (T, P, xi ) mix (8.2-3)

By denition, excess properties are zero for an ideal mixture. They are only dened for mixtures2 and have no physical meaning for pure uids. Dividing each term in Eq. (8.2-2) by the total number of moles gives the molar property of the mixture as k X xi i + e IM + ex e mix e (8.2-4) mix = e For a binary mixture, a representative plot of mix as a function of composition is shown in e Figure 8.2.

% mix % ex

i=1 |

IM e mix

{z

% IM mix

x1

The relationship between the excess property and the property change on mixing can be found from Eq. (8.2-1) as e e IM e e V ex = Vmix Vmix = Vmix | {z }

0

(8.2-5) (8.2-6)

k X i=1

e ex

0

xi ln xi

(8.2-7)

Partial molar excess functions are dened in a manner analogous to that used for partial molar properties, i.e., ex ex i = (8.2-9) ni T,P,nj6=i Thus, substitution of Eq. (8.2-3) into Eq. (8.2-9) gives IM mix mix ex = i ni T,P,nj6=i ni T,P,nj6=i = i IM i

2

k X i=1

xi ln xi

(8.2-8)

(8.2-10)

This is the reason why an excess property is designated as ex and not as ex . mix

217

8.2.1 Relations Between Excess Properties For a single phase, multicomponent open system the dierential change in the Gibbs energy is given by Eq. (7.1-13), i.e., k X dG = V dP S dT + Gi dni (8.2-11)

i=1

ex

=V

ex

dP S

ex

dT +

k X i=1

Gi dni

ex

(8.2-12)

i=1 k ex

(8.2-13)

Gex RT

1 Gex dGex dT RT RT 2

(8.2-14)

XG V ex H ex i dP dni dT + RT RT 2 RT

i=1

ex

(8.2-15)

which is known as the fundamental excess-property relation. Dierentiation of Eq. (8.2-15) with respect to pressure by keeping temperature and the mole numbers of all components constant gives (Gex /RT ) V ex (8.2-16) = P RT T,nj or e Gex P ! e = V ex

(8.2-17)

T,xj

Dierentiation of Eq. (8.2-15) with respect to temperature by keeping pressure and the mole numbers of all components constant gives (Gex /RT ) H ex = (8.2-18) T RT 2 P,nj or " T e Gex T !# e H ex T2

P,xj

(8.2-19)

which is simply the extension of the Gibbs-Helmholtz equation, Eq. (5.7-8), to excess quantities. Once molar excess Gibbs energy is known, molar excess volume (or volume change on mixing) and molar excess enthalpy (or enthalpy change on mixing) can be evaluated by using

218

e e Eqs. (8.2-17) and (8.2-19), respectively. On the other hand, U ex and S ex can be calculated from the following equations: e e e (8.2-20) U ex = H ex P V ex e e H ex Gex e S ex = T T (8.2-21)

Example 8.1 A stream of liquid 1 owing at 5 mol/ s and a stream of liquid 2 owing at 3 mol/ s, both at 298 K, are mixed in a steady ow process. For this mixture the molar excess Gibbs energy is given by e Gex = A x1 x2 RT in which the parameter A is given as a function of temperature in the form A = 14.8 where T is in K. a) How much heat must be added to or removed from the mixer so as to maintain the mixing process isothermal? b) Suppose that the entering temperature of liquid 2 is increased from 298 K to 330 K and the mixer is adiabatic. Determine the temperature of the stream leaving the mixer under these e e conditions. Take pure component heat capacities as CP1 = 35 J/ mol. K and CP2 = 50 J/ mol. K. n1 + n2 = nmix and H = Q + Ws |{z}

0

1000 2 ln T T

Solution

a) Considering the mixer as a system, the mass and energy balances are (1) (2)

Substitution of Eqs. (1) and (2) into Eq. (3) and using the relationship nmix xi = ni yield e e e e Q = n1 H1 + n2 H2 + (n1 + n2 ) Hmix (n1 H1 + n2 H2 ) e e e = (n1 + n2 ) Hmix = (n1 + n2 ) H ex (5) i = 1, 2 (4)

e e e e Hmix = x1 H1 + x2 H2 + Hmix

(3)

dA e = R x1 x2 (2 T 1000) H ex = RT 2 x1 x2 dT Substitution of the numerical values gives h i 3 e ex = (8.314) 5 (2)(298) 1000 = 787.2 J/ mol H 8 8 219

(6)

Thus, the amount of heat that must be removed from the system is calculated as Q = (8)( 787.2) = 6298 W b) Since the mixer is adiabatic, i.e., Q = 0, Eq. (2) becomes e H = nmix Hmix n1 H1 + n2 H2 e e

T 298

330

Substitution of Eqs. (1) and (8) into Eq. (7) and rearrangement lead to e e e e e + n2 H2 H2 + (n1 + n2 ) Hmix = 0 n1 H1 H1

T 298 T 330 T

where T represents the temperature of the stream leaving the mixer. The molar enthalpy of the mixture, Eq. (3), is given by e e e e (8) Hmix = x1 H1 + x2 H2 + Hmix

T T T T

=0

(7)

(9)

e e e e e Since H = CP T (assuming constant CP ) and Hmix = H ex , Eq. (9) becomes 3 5 (2 T 1000) = 0 (5)(35)(T 298) + (3)(50)(T 330) + (8)(8.314) 8 8 n1 CP1 (T 298) + n2 CP2 (T 330) + (n1 + n2 ) R x1 x2 (2 T 1000) = 0 e e

or

8.3 ACTIVITY AND ACTIVITY COEFFICIENT In a multicomponent mixture, the activity of component i, bi , is dened as a bi (T, P, xi ) = a b fi (T, P, xi ) b f o (T o , P o , xo )

i i

(8.3-1)

where the superscript o implies the standard state. Among the various standard states used in the literature, the most commonly used standard state is the pure component, i.e., xo = 1, at i the same temperature, pressure, and phase as the mixture. Under these conditions, Eq. (8.3-1) becomes b fi (T, P, xi ) (8.3-2) bi (T, P, xi ) = a fi (T, P ) For an ideal mixture, application of the Lewis-Randall rule simplies Eq. (8.3-2) to bIM = xi ai (8.3-3)

The activity coecient, , is dened to account for the deviation from an ideal mixture behavior, i.e., bi = i xi a (8.3-4) Comparison of Eqs. (8.3-2) and (8.3-4) leads to i (T, P, xi ) = b b fi (T, P, xi ) fi (T, P, xi ) = xi fi (T, P ) bIM f (T, P, xi )

i

(8.3-5)

220

From Eq. (8.3-5), it is obvious that i 1 as xi 1. b For a binary liquid mixture, representative plots of fugacity of component 1, f1 , versus the mole fraction of 1, x1 , are shown in Figure 8.3 by solid curves. When the Lewis-Randall rule is applicable, fugacity of component 1 varies linearly with mole fraction as shown by a dashed straight line. When xi 1, the solid curve coincides with the dashed straight line.

f1 1 1 f1 f1 1 1 IM = f x f1 1 1 f1

IM = f x f1 1 1

x1 (a)

x1 (b)

Figure 8.3 Variation of fugacity of component 1 in a liquid mixture with composition. b bIM Since f1 > f1 in Figure 8.3-a, the activity coecient is greater than unity when 0 < x1 < 1. The higher the activity coecient (or activity), the higher the escaping tendency of a component from the liquid phase. Thus, 1 > 1 can be regarded as a form of repulsion between unlike molecules in a liquid mixture. In other words, the like interactions are stronger than the bIM b unlike interactions. In Figure 8.3-b, on the other hand, f1 < f1 and the activity coecient is less than unity when 0 < x1 < 1. In this case, component 1 prefers to remain in the liquid phase since the unlike interactions are stronger than the like interactions. 8.3.1 Relationship Between Activity Coecients and Excess Properties Using Eq. (8.2-10), partial molar excess Gibbs energy is expressed as

ex Gi

IM Gi Gi

ex

b b = i + RT ln fi i + RT ln fiIM = RT ln Gi = RT ln i

b fi bIM f

i

(8.3-6)

(8.3-7)

Note that activity coecients are dependent on temperature, pressure, and composition of the mixture. The limiting values of the activity coecients are given as 1 xi 1 (8.3-8) i = xi 0 i where is the activity coecient of component i at innite dilution. It reects the behavior i of a single solute molecule completely surrounded by solvent. Figure 8.4 shows how activity coecients vary with composition in a binary mixture. The molar excess Gibbs energy is given by e Gex =

k X i=1

xi Gi

ex

(8.3-9)

221

2 1

x1

Figure 8.4 A typical plot showing variation of activity coecients with composition. Substitution of Eq. (8.3-7) into Eq. (8.3-9) gives e Gex = RT 8.3.2 Estimation of Excess Properties For liquid mixtures, experimental determinations of volume change on mixing and heat of mixe e e e ing were explained in Section 6.3. Since Vmix = V ex and Hmix = H ex , then experimental ex and H ex are rather straightforward. e e determinations of V According to Eq. (8.3-10), evaluation of molar excess Gibbs energy requires experimental determination of activity coecients. Activity coecients are calculated from the experimental vapor-liquid equilibrium (VLE) measurements. At equilibrium, fugacities of each component in the vapor and liquid phases must be equal to each other, i.e., b b fiV (T, P, yi ) = fiL (T, P, xi ) bV i (T, P, yi ) yi P = fiL (T, P ) i (T, P, xi ) xi = Pivap V (T, Pivap ) exp i e ViL (P Pivap ) RT (8.3-11)

k X i=1

xi ln i

(8.3-10)

or

When pressure is not very high, the Poynting correction factor is almost unity and the vapor bV phase can be considered an ideal gas mixture, i.e., i (T, P, yi ) = 1 and V (T, Pivap ) = 1. In i other words, nonidealities associated with the vapor phase are neglected3 and the liquid phase nonideality is represented by the activity coecient. With such simplications, Eq. (8.3-12) reduces to i = yi P xi Pivap (8.3-13)

i (T, P, xi ) xi

(8.3-12)

The procedure for expressing molar excess Gibbs energy as a function of composition can be outlined as follows:

It should be kept in mind that the vapor phase nonideality cannot be neglected at all times, especially when pressure is moderate or high. See Example 8.6 and Problem 8.10 for further details.

3

222

At a specied temperature, let the vapor and liquid phases of a multicomponent mixture reach equilibrium and record the pressure (isothermal data); or, at a specied pressure, let the vapor and liquid phases of a multicomponent mixture reach equilibrium and record the temperature (isobaric data), Take small samples from the liquid and vapor phases and determine xi and yi , Using the Antoine equation calculate Pivap at the specied (or recorded) temperature, Use Eq. (8.3-13) and calculate i values, e Calculate Gex from Eq. (8.3-10), e Develop a mathematical equation for expressing Gex as a function of xi . Note that the eex should satisfy the fact that expression for G e For a binary mixture, Gex /RT is generally expressed4 as a function of composition using a Redlich-Kister type expansion, i.e.,

n X e Gex = x1 x2 Ai (x1 x2 )i1 RT i=1

(8.3-14)

(8.3-15)

Example 8.2 Huang et al. (2004) reported the following vapor-liquid equilibrium data for tetraethyl orthosilicate (1)ethanol (2) mixtures at 400 mmHg: T ( K) 336.5 337.9 339.5 344.4 360.8 x1 0.0000 0.1622 0.2721 0.5132 0.8252 y1 0.0000 0.0144 0.0205 0.0352 0.1170 T ( K) 378.2 398.7 410.0 419.2 x1 0.9061 0.9668 0.9892 1.0000 y1 0.2211 0.4953 0.7370 1.0000

The vapor pressures of pure components are given by the Antoine equation as

vap ln P1 = 16.784

3942.79 T 53.797

and

vap ln P2 = 20.421

4657.84 T 13.722

e where P is in mmHg and T is in K. Calculate the activity coecients and express Gex /RT as a function of composition.

4

e In the literature, the term Gex /RT is sometimes expressed in the form

n X e Gex = x1 x2 Ai Li (x1 ) RT i=0

where Li s are the Legendre polynomials given by Li (x1 ) = in which Lo (x1 ) = 1 and L1 (x1 ) = 2 x1 1 (2i 1)(2x1 1) Li1 (x1 ) (i 1) Li2 (x1 ) i

223

Solution At each temperature, vapor pressures are calculated from 3942.79 4657.84 vap vap P2 = exp 20.421 P1 = exp 16.784 T 53.797 T 13.722 The activity coecients are then calculated by using Eq. (8.3-13), i.e., 1 = y1 P

vap x1 P1

and

2 =

y2 P

vap x2 P2

e Finally, the term Gex /RT is determined from Eq. (8.3-10) as The results are tabulated below: e Gex = x1 ln 1 + x2 ln 2 RT

vap P1 ( mmHg)

vap P2 ( mmHg)

5 X e Gex = x1 x2 Ai (x1 x2 )i1 RT i=1

with A1 = 0.914, A2 = 0.532, A3 = 1.957, A4 = 1.918, and A5 = 2.889. Sometimes an equation relating molar excess Gibbs energy to the composition in the form e Gex = f (x1 , x2 , ..., xk ) RT (8.3-16)

is given and it is required to calculate the activity coecients. For this purpose, the use of Eq. (8.3-7) in Eq. (8.2-15) results in d Gex RT = X V ex H ex dP dT + ln i dni 2 RT RT

i=1 k

(8.3-17)

224

T,P,nj6=i

implying that ln i can be interpreted as the partial molar property of Gex /RT . Examination of Eqs. (8.2-16), (8.2-18), and (8.3-18) reveals that excess Gibbs energy can be regarded as a generating function to estimate other excess properties as shown in Figure 8.5.

/ ni / P

ln i

Gex / RT

V ex / RT

/ T

Hex / RT2

Figure 8.5 Partial dierentiation of Gex /RT leads to various excess quantities. e For a binary mixture, taking mix = Gex /RT and i = ln i , the use of Eqs. (6.2-24) and e (6.2-25) leads to the following equations for the evaluation of activity coecients: e d Gex x2 ln 1 = RT dx2 e d Gex x1 ln 2 = RT dx1 e Gex RT e Gex RT ! ! (8.3-19)

(8.3-20)

e In other words, intercepts of the tangent to the Gex /RT versus x1 (or x2 ) curve at x1 = 1 and x1 = 0 give ln 1 and ln 2 , respectively. e When Gex /RT is expressed by Eq. (8.3-15), Eqs. (8.3-19) and (8.3-20) yield ln 1 = x2 2

n X i=1 n X i=1

Ai (x1 x2 )i1 + 2 x1 x2 2

i1

n1 X i=1 n1 X i=1

(8.3-21)

ln 2 =

x2 1

Ai (x1 x2 )

2 x2 x2 1

(8.3-22)

8.3.3 Variation of Activity Coecients with Temperature It follows from Eq. (8.2-19) that " T Gi RT

ex

!#

P,xj

H = i2 RT

ex

(8.3-23)

225

ex

(8.3-24)

For small temperature changes, partial molar excess enthalpy, H i , may be considered constant. In this case, integration of Eq. (8.3-24) at constant pressure and composition gives Hi i (T2 , P, xi ) = i (T1 , P, xi ) exp R Partial molar excess enthalpy is calculated from

ex e H i = H i Hi

"

ex

1 1 T2 T1

(8.3-25)

(8.3-26)

Once heat of mixing is determined experimentally, partial molar excess enthalpy can be easily ex determined as explained in Problem 8.5. Note that when H i is of the order of 104 J/ mol or greater, the exponential term in Eq. (8.3-25) is dierent from unity. 8.3.4 Variation of Activity Coecients with Pressure It follows from Eq. (8.2-17) that Gi P

ex

=Vi

ex

(8.3-27)

T,xj

ex

(8.3-28)

The partial molar excess volume of component i in the mixture, V i , is usually pressure independent. As a result, integration of Eq. (8.3-28) at constant temperature and composition gives # " ex V i (P2 P1 ) i (T, P2 , xi ) = i (T, P1 , xi ) exp (8.3-29) RT Partial molar excess volume is calculated from

ex e V i = V i Vi

(8.3-30)

Example 8.3 Using the data given in Problem 6.22, estimate partial molar excess volumes for a mixture of methanol (1) and benzene (2) at 298 K. Show that the exponential correction term in Eq. (8.3-29) is almost unity. Solution Partial molar volumes of methanol and benzene can be determined from Eqs. (2) and (3) of Problem 6.22, respectively, as e V 1 = V1 + x2 2

4 X i=1

Ai (x1 x2 )

i1

+ 2 x1 x2 2

3 X i=1

(1)

226

The use of Eqs. (1) and (2) in Eq. (8.3-30) gives partial molar excess volumes as V 1 = x2 2

ex 4 X i=1 4 X i=1

e V 2 = V2 + x2 1

4 X i=1

Ai (x1 x2 )i1 2 x2 x2 1

3 X i=1

(2)

3 X i=1 3 X i=1

(3)

V 2 = x2 1

ex

(4)

ex

A2 = 0.1342

ex

A3 = 0.1740

A4 = 0.1906

The calculated values of V 1 and V 2 as a function of composition are given in the following table: x1 0.0 0.1 0.2 0.3 0.4 0.5

ex

ex

ex

ex

ex

Comment: Assuming activity coecients to be independent of pressure is plausible even at high pressures.

Note that V i is of the order of 101 cm3 / mol. Taking P2 P1 = 500 bar, the exponential term in Eq. (8.3-29) becomes (0.1)(500) = 1.002 " ex # exp (83.14)(298) V i (P2 P1 ) exp = RT exp ( 0.1)(500) = 0.998 (83.14)(298)

8.4 BINARY ACTIVITY COEFFICIENT MODELS Activity coecient models can be broadly classied as follows: Empirical models: The molar excess Gibbs energy is expressed as e Gex = x1 x2 f (x1 , x2 ) RT

and activity coecients are determined from Eqs. (8.3-19) and (8.3-20). The parameters appearing in these equations are estimated with the help of experimental data. Some examples are two- and three-sux Margules equations, and the van Laar equation. 227

Local composition models: These models assume that the bulk (or mean) concentration of species in solution is very dierent from the local concentration. Hence, local concentrations are dependent on the interactions between molecules and a radial distribution function. Some examples are Wilson (Wilson, 1964), NRTL - NonRandom Two-Liquid (Renon and Prausnitz, 1968), and UNIQUAC - UNIversal QUAsi-Chemical (Abrams and Prausnitz, 1975). Group contribution models: These models are based on the molecular structure. The activity coecients are estimated by the additive contributions of the functional groups comprising the molecule. Some examples are UNIFAC - UNIed Activity Coecient (Fredenslund et al., 1975), Modied UNIFAC - Dortmund (Weidlich and Gmehling, 1987), and ASOG Analytical Solutions of Groups (Kojima and Tochigi, 1979). Coverage of all activity coecient models available in the literature is beyond the scope of this text. In the following section, some of the most commonly used activity coecient models for binary liquid mixtures will be briey given. 8.4.1 Two-Sux5 (One-Constant) Margules Equation This is the simplest empirical model, in which molar excess Gibbs energy is proposed in the form e Gex = A x1 x2 (8.4-1) RT

In other words, i = 1 in the Redlich-Kister expansion, Eq. (8.3-15). Substitution of Eq. (8.4-1) into Eqs. (8.3-19) and (8.3-20) gives the activity coecients as ln 1 = A x2 2 ln 2 = A x2 1

(8.4-2) (8.4-3)

Representative plots of 1 and 2 as a function of composition are given in Figure 8.6. Since e the function representing Gex is symmetric, then the activity coecients are mirror images of each other.

ln i

ln 1 ln 2

0 0 x1 1

Figure 8.6 Binary activity coecients for the two-sux Margules equation. In general, the parameter A is dependent on temperature and pressure, and related to the logarithm of the activity coecients at innite dilution as A = ln = ln 1 2

5

(8.4-4)

e Two-sux implies that the expansion for Gex is quadratic in mole fraction.

228

When A is positive, activity coecients are greater than unity, and like interactions are much greater than unlike interactions. On the other hand, when A is negative, activity coecients are less than unity, and unlike interactions are stronger than like interactions. The two-sux Margules equation applies best to mixtures of simple molecules of similar size, shape, and chemical nature. For example, argon-oxygen (liquid mixture in cryogenic applications) and benzene-cyclohexane mixtures can be described by this model. Example 8.4 Derive Eqs. (8.4-2) and (8.4-3). Solution Equation (8.4-1) can be expressed as n n e Gex 1 2 =A RT n n (1)

where n = n1 + n2 is the total number of moles. The total excess Gibbs energy, Gex , is ! e Gex Gex n1 n2 =n =A RT RT n1 + n2 From Eqs. (8.3-19) and (8.3-20) (Gex /RT ) ln 1 = n1 (Gex /RT ) ln 2 = n2 =A n2 2 (n1 + n2 )2 n2 1 (n1 + n2 )2 = A x2 2

(2)

(3)

T,P,n2

=A

= A x2 1

(4)

T,P,n1

Alternate solution: Substitution of Eq. (8.4-1) into Eqs. (8.3-19) and (8.3-20) leads to ln 1 = Ax1 x2 Ax2 ( x2 + x1 ) = A x2 2 ln 2 = Ax1 x2 Ax1 (x2 x1 ) = A x2 1 (5) (6)

Example 8.5 Mara et al. (1997) obtained the following set of vapor-liquid equilibrium data for the 1-propanol (1) and 2-pentanol (2) system at 313.5 K: x1 0.2022 0.4030 0.6026 0.8015 y1 0.4332 0.6784 0.8282 0.9278 P ( kPa) 3.189 4.154 5.097 6.026

If the two-sux Margules equation represents this system, calculate the parameter A. The vapor pressures of 1-propanol and 2-pentanol at 313.5 K are 6.970 kPa and 2.261 kPa, respectively.

229

Solution The parameter A in the two-sux Margules equation is given by A= e Gex /RT x1 x2 (1)

e Therefore, it is necessary to calculate Gex /RT as a function of composition from Eq. (8.3-10), i.e., e Gex (2) = x1 ln 1 + x2 ln 2 RT The activity coecients, on the other hand, are calculated by using Eq. (8.3-13), i.e., 1 = y1 P

vap x1 P1

and

2 =

y2 P

vap x2 P2

(3)

The results are given in the following table: x1 0.2022 0.4030 0.6026 0.8015 y1 0.4332 0.6784 0.8282 0.9278 1 0.980 1.003 1.005 1.001 2 1.002 0.990 0.975 0.969 e (Gex /RT ) 103 2.243 4.863 7.204 5.527 A 0.015 0.020 0.030 0.035

Taking the arithmetic average of A gives 0.015 + 0.020 + 0.030 + 0.035 = 0.025 A= 4 Alternate solution: The parameter A can also be determined by dening an "objective function". For example, an objective function, F , with respect to molar excess Gibbs energy is dened as !2 4 X Gex e A x1 x2 F = RT

i=1 i

The value of A that minimizes the sum of the squares of the deviations is given by !2 4 e d X Gex A x1 x2 =0 dA RT

i=1 i

or

A=

4 X i=1

4 X i=1

e Gex x1 x2 RT (x1 x2 )2 i

A = 0.027

230

8.4.2 Three-Sux6 (Two-Constant) Margules Equation In this empirical model the expression for molar excess Gibbs energy is given by7 e Gex = x1 x2 A + B(x1 x2 ) RT (8.4-5)

In other words, i = 2 in the Redlich-Kister expansion, Eq. (8.3-15). The use of Eq. (8.4-5) in Eqs. (8.3-19) and (8.3-20) gives the activity coecients as ln 1 = x2 (A + 3 B 4 Bx2 ) 2 ln 2 = x2 (A 3 B + 4 Bx1 ) 1 Linearization of Eq. (8.4-5) gives e Gex /RT = 2B x1 + (A B) x1 x2 (8.4-8) (8.4-6) (8.4-7)

e so that the parameters A and B can be determined graphically8 , i.e., a plot of (Gex /RT )/x1 x2 versus x1 gives a straight line with a slope of 2B and an intercept of (AB) as shown in Figure 8.7.

% Gex / RT x1x 2

ln 1

= A B

Slope = 2B

ln = A + B 2 1

x1

Figure 8.7 A binary liquid mixture represented by the three-sux Margules equation. The innite dilution activity coecients can be obtained from Eq. (8.4-6) as x1 0 and from Eq. (8.4-7) as x2 0. The resulting expressions are ln = A B 1

6 7

and

ln = A + B 2

(8.4-9)

e Three-sux implies that the expansion for Gex is third-order in mole fraction. For an alternate expression of molar excess Gibbs energy, see Problem 8.12. 8 Graphical determination of parameters A and B is also possible by linearizing Eq. (8.4-6), i.e., ln 1 x2 or by linearizing Eq. (8.4-7), i.e., = 4Bx1 + (A 3B) 2 x1 For a more thorough discussion on the subject, see Shacham et al. (1993). ln 2

2

= 4B x2 + (A + 3B)

231

Example 8.6 Gabaldon et al. (1996) obtained the following set of data for the water (1) and n-propanol (2) system at 0.6 bar: x1 0.103 0.231 0.294 0.361 0.487 1 3.107 2.603 2.397 2.212 1.814 2 1.011 1.051 1.083 1.158 1.306 x1 0.557 0.686 0.796 0.869 1 1.642 1.385 1.203 1.099 2 1.443 1.925 2.850 4.294

Thus, the parameters A and B are expressed in terms of the activity coecients at innite dilution as s p 2 A = ln 1 2 and B = ln (8.4-10) 1

Estimate the Margules parameters A and B, and calculate the innite dilution activity coecients. Solution The molar excess Gibbs energy is calculated from Eq. (8.3-10), i.e., e Gex = x1 ln 1 + x2 ln 2 RT and the values are given in the table below: x1 0.103 0.231 0.294 0.361 0.487 e Gex /RT 0.127 0.259 0.313 0.380 0.427 x1 0.557 0.686 0.796 0.869 e Gex /RT 0.439 0.429 0.361 0.273

e The plot of (Gex /RT )/x1 x2 versus x1 is shown below. The data t a straight line with a correlation coecient9 of 0.979.

2.5 2.398

2 y z 1.5

1.284 1 0 0.103

9

0.2

0.4 x1

0.6

0.8 0.869

A correlation coecient measures the degree to which two variables are directly related. Its value changes from 1 to 1, 1 and 1 being perfect negative and positive correlations, respectively.

232

The slope and the intercept of the best straight line passing through the data points are 1.309 and 1.150, respectively. Therefore, the parameters are A = 1.805 and B = 0.655

The use of Eq. (8.4-9) gives the innite dilution activity coecients as = 3.158 1 and = 11.705 2

Alternate solution: The parameters A and B can also be determined by dening an objective function, F , as ( ) 9 h i 2 X Gex e x1 x2 A + B(x1 x2 ) F = RT

i=1 i

The values of A and B that minimize the sum of the squares of the deviations are given by ( ) 9 h i 2 e X Gex x1 x2 A + B(x1 x2 ) =0 (1) A RT

i=1 i 9 X B i=1

Once the derivations are carried out, Eqs. (1) and (2) take the form ! 9 9 9 i X Xh X Gex e (x1 x2 )i + B A x1 x2 (x1 x2 ) = RT i

i=1 i=1 i=1

e Gex RT

) h i 2 x1 x2 A + B(x1 x2 ) =0

i

(2)

(3) !

Using matrix algebra, the parameters A and B can be determined from Eqs. (3) and (4) as ! 1 9 9 9 X X X Gex e (x1 x2 )i x1 x2 (x1 x2 ) i i=1 RT i=1 i=1 i A = ! B 9 9 9 X X e X Gex x1 x2 x1 x2 (x1 x2 ) i x1 x2 (x1 x2 )2 i RT

i=1 i=1 i=1 i

9 Xh i=1

e Gex x1 x2 RT

(4)

1.696 0.037

0.037 0.315

3.008 0.139

1.788 0.651

which are slightly lower than the previously calculated values. The parameters A ln 2 A= 2 2 x1 x1 and B can be estimated from a single set of activity coecient data as ! ln 1 3 1 1 ln 1 ln 2 2 x1 2 and B= (8.4-11) + 2 2 2 2 2 x2 x2 x1

Example 8.7 The following vapor-liquid equilibrium data are provided for a binary mixture of ethanol (1) and acetone (2) by Campbell et al. (1987):

233

T ( K) 397.7 At 397.7 K

vap P1 = 487.1 kPa

P ( kPa) 652.9

x1 0.342

y1 0.305

The vapor phase obeys the virial equation of state with the following parameters: B11 = 562.3 cm3 / mol B12 = 519.6 cm3 / mol

If the liquid mixture is represented by the three-sux Margules equation, estimate the parameters A and B. Solution Once the activity coecients, 1 and 2 , are calculated at the given experimental data point, the parameters A and B can be determined from Eq. (8.4-11). The starting point for the calculation of activity coecients is Eq. (8.3-12), i.e., bV i (T, P, yi ) yi P = fiL (T, P ) i (T, P, xi ) xi = Pivap V (T, Pivap ) exp i

e ViL (P Pivap ) RT

Since pressure is high, simplifying assumptions of this equation leading to Eq. (8.3-13) are no longer valid. Therefore, activity coecients are calculated from Eq. (1) as bV i (T, P, yi ) yi P h i i = vap V vap e L (P P vap )/RT Pi i (T, Pi ) xi exp Vi i = exp

vap B11 P1

i (T, P, xi ) xi

i = 1, 2

(1)

(2)

vap V (T, P1 ) 1

RT

vap B22 P2

! !

vap V (T, P2 ) 2

= exp

RT

From Eq. (7.5-6) i h bV = exp P B11 + y 2 (2 B12 B11 B22 ) 1 2 RT n o 652.9 562.3 + (0.695)2 [2 (519.6) + 562.3 + 692.9] = exp = 0.914 (8314)(397.7) bV 2 = exp i P h 2 B22 + y1 (2 B12 B11 B22 ) RT n o 652.9 2 692.9 + (0.305) [2 (519.6) + 562.3 + 692.9] = exp = 0.876 (8314)(397.7) 234

The Poynting correction factors for ethanol and acetone are vap e V1L (P P1 ) (67.4)(652.9 487.1) = exp = 1.003 exp RT (8314)(397.7) exp

vap e V2L (P P2 )

RT

Substitution of the numerical values into Eq. (2) gives the activity coecients as 1 = 2 = (0.914)(0.305)(652.9) = 1.183 (487.1)(0.921)(0.342)(1.003) (0.876)(0.695)(652.9) = 1.044 (665.3)(0.870)(0.658)(1.000)

The use of Eq. (8.4-11) gives the parameters as ln(1.044) ln(1.183) 3 1 A= + 2(0.342) = 0.384 2(0.342) (0.342)2 2 (0.658)2 2 1 ln(1.183) ln(1.044) B= = 0.010 2 (0.658)2 (0.342)2 Comment: One should be cautious in using parameters based on a single set of experimental data.

The three-sux Margules equation can be used to model moderately nonideal mixtures. 8.4.3 van Laar Equation The van Laar equation, like the three-sux Margules equation, is another two-parameter empirical model in which molar excess Gibbs energy is represented by10 e AB Gex = x1 x2 RT Ax1 + Bx2 The use of Eq. (8.4-12) in Eqs. (8.3-19) and (8.3-20) gives the activity coecients as A ln 1 = A x1 2 1+ B x2 B ln 2 = B x2 2 1+ A x1

10

(8.4-12)

(8.4-13)

(8.4-14)

235

e so that the parameters A and B can be determined graphically11 , i.e., a plot of x1 /(Gex /RT ) versus x1 /x2 gives a straight line with a slope of 1/B and an intercept of 1/A as shown in Figure 8.8.

x1 / RT

% ex

1 1 = A ln1

1 1 = B ln 2

slope =

x1 x2

Figure 8.8 A binary liquid mixture represented by the van Laar equation. The parameters A and B can also be estimated from a single set of activity coecient data as x2 ln 2 2 A = ln = ln 1 1 + 1 x1 ln 1 and x1 ln 1 2 B = ln = ln 2 1 + (8.4-16) 2 x2 ln 2

The van Laar model is adequate for moderately nonideal mixtures, but cannot be used for highly nonideal mixtures. In most cases, the parameters A and B are dicult to estimate as a result of the lack of reliable experimental data. For nonpolar binary mixtures, the van Laar equation can be reduced to a one-parameter form by replacing the ratio A/B by the the ratio of molar liquid volumes (Reid et al., 1987), i.e., e V1L A = L (8.4-17) B e V2

11

Such simplication, however, cannot be used if one of the components is polar. Molar liquid volumes can be calculated by the use of the modied Rackett equation, Eq. (5.4-9).

Graphical determination of parameters A and B is also possible by linearizing Eq. (8.4-13), i.e., 1 1 A x1 p = + B x2 ln 1 A 1 1 B x2 p = + A x1 ln 2 B

For a more thorough discussion on the subject, see Shacham et al. (1993).

236

Example 8.8 For a binary mixture of carbon tetrachloride (1) and n-propanol (2), Carley and Bertelsen (1949) obtained the following data from VLE experiments under atmospheric pressure: x1 0.058 0.141 0.300 1 2.90 2.51 2.00 2 1.03 1.06 1.15 x1 0.441 0.522 0.683 1 1.64 1.50 1.24 2 1.29 1.40 1.84 x1 0.818 0.851 0.950 1 1.10 1.07 1.013 2 2.73 3.05 5.54

Which model, three-sux Margules or van Laar, better represents the activity coecients of this system? Solution The molar excess Gibbs energy is calculated from Eq. (8.3-10), i.e., e Gex = x1 ln 1 + x2 ln 2 RT

e If the system is represented by the three-sux Margules equation, then the plot of (Gex /RT )/x1 x2 versus x1 should yield a straight line. In the gure shown below, the correlation coecient of the best straight line passing through the data points is 0.698. The scatter of the data indicates that the representation of this binary system by the three-sux Margules equation is rather poor.

2.2 2.06

w f 1.8

1.6

On the other hand, if the activity coecients are represented by the van Laar model, then the e plot of x1 /(Gex /RT ) versus x1 /x2 should yield a straight line. The gure shown below yields almost a straight line with a correlation coecient of 0.998. The slope and the intercept of the straight line are 0.473 and 0.852, respectively.

10 9.834 8

z f

2 0.647 0 0 0.062 5 10 v 15 19 20

237

Therefore, the system is best represented by the van Laar model and the parameters are A = 1.174 and B = 2.114

8.4.4 Wilson Equation The Wilson equation is based on a local composition model and the molar excess Gibbs energy is given by e Gex = x1 ln (x1 + 12 x2 ) + x2 ln (x2 + 21 x1 ) (8.4-18) RT The use of Eq. (8.4-18) in Eqs. (8.3-19) and (8.3-20) gives the activity coecients as ln 1 = ln (x1 + 12 x2 ) + x2 ln 2 = ln (x2 + 21 x1 ) + x1 21 12 x2 + 21 x1 x1 + 12 x2 12 21 x1 + 12 x2 x2 + 21 x1 (8.4-19)

(8.4-20)

The parameters 12 and 21 can be evaluated as follows12 : In terms of the innite dilution activity coecients, Eqs. (8.4-19) and (8.4-20) reduce to ln = ln 12 + 1 21 1 ln = ln 21 + 1 12 2 Equations (8.4-21) and (8.4-22) can be reduced to a single equation of the form 1 1 12 = exp 1 exp (1 12 ) 1 2 so that 12 can be determined. Then the parameter 21 is calculated from 21 = 1 ln (12 ) 1 (8.4-24) (8.4-21) (8.4-22)

(8.4-23)

The evaluation of 12 and 21 from Eqs. (8.4-23) and (8.4-24) is not straightforward when one of the innite dilution activity coecients (or both) is less than unity. In that case the solution of Eq. (8.4-23) yields multiple roots. It should be kept in mind that the Wilson parameters cannot be negative (Why?). Example 8.9 For a binary system of thiophene (1) and n-hexane (2), Sapei et al. (2006) reported = 1.82 and = 2.49 at 338.15 K. If this system is represented by the Wilson 1 2 equation, evaluate the parameters 12 and 21 , and express activity coecients as a function of mole fractions. Solution The use of Eq. (8.4-23) gives 12

12

12 ' 1

238

Then the parameter 21 can be estimated from Eq. (8.4-24) as 21 = 1 ln (1.82) = 0.4 Thus, Eqs. (8.4-19) and (8.4-20) take the form ln 1 = x2 1 0.4 x2 + 0.4 x1 0.4 ln 2 = ln (x2 + 0.4 x1 ) + x1 1 x2 + 0.4 x1 The numerical values of the activity coecients are given in the table below : x1 0.1 0.2 0.3 0.4 0.5 1 1.677 1.547 1.431 1.329 1.239 2 1.004 1.019 1.046 1.089 1.153 x1 0.6 0.7 0.8 0.9 1 1.162 1.098 1.047 1.013 2 1.248 1.387 1.599 1.933

In the literature, the parameters 12 and 21 are usually expressed as 12 12 11 = L exp RT e V1 e V2L and 21 21 22 = L exp RT e V2 e V1L (8.4-25)

where ij s are the energy parameters associated with the interaction between molecules i and j. In most applications, the parameters (12 11 ) and (21 22 ) are considered independent e of temperature. The molar volume of pure liquid i, ViL , can be estimated by the modied Rackett equation, Eq. (5.4-9). The Wilson equation can be used when the components in the liquid phase are completely miscible over the whole composition range. For example, it works well for mixtures of highly polar compounds, i.e., alcohol and water, and mixtures of hydrocarbons. 8.4.5 NRTL (Nonrandom Two-Liquid) Equation The NRTL equation, which is based on a local composition model, is proposed in the form e 21 G21 12 G12 Gex = x1 x2 + RT x1 + G21 x2 x2 + G12 x1 where G12 = exp ( 12 ) g12 g22 RT and G21 = exp ( 21 ) g21 g11 RT (8.4-27) The parameters 12 and 21 are expressed in terms of the energy parameters, gij , in the form 12 = and 21 = (8.4-28) (8.4-26)

The use of Eq. (8.4-26) in Eqs. (8.3-19) and (8.3-20) leads to the following activity coecients: " # 2 G21 12 G12 ln 1 = x2 21 + (8.4-29) 2 x1 + G21 x2 (x2 + G12 x1 )2 239

ln 2 = x2 12 1

"

G12 x2 + G12 x1

(8.4-30)

The use of the NRTL equation requires two temperature-dependent parameters, 12 and 21 , in addition to a nonrandomness parameter13 , . Comparison with the experimental VLE data indicates that values change between 0.2 and 0.47. Thus, in the absence of information, it is generally recommended to take = 0.3 in the calculations. At innite dilution, and when is estimated, Eqs. (8.4-29) and (8.4-30) can be reduced to a single equation when 21 from 21 = ln 12 exp ( 12 ) 1 is substituted into 12 = ln 21 exp ( 21 ) 2 (8.4-32) The NRTL equation can be used for highly nonideal systems as well as for partially miscible systems. Among the various activity coecient models discussed above, the Wilson model usually provides the best combination of ease of use and accuracy, as long as there is no miscibility problem. If limited solubility is a problem, then the NRTL model should be used. 8.5 REGULAR MIXTURE As dened in Section 7.4, an ideal mixture is one in which molecules are of the same size and shape, and the interactions between unlike molecules are, more or less, the same as those between like molecules. Thus, molar excess Gibbs energy, like all other excess properties, is zero for an ideal mixture. A regular mixture, on the other hand, is dened as the one in which excess volume and excess entropy are both zero. Since Gex = H ex T S ex = U ex +P V ex T S ex , it follows that Gex = H ex = U ex Regular mixture (8.5-1) "Regular mixture" approximation relaxes one of the assumptions of an "ideal mixture", i.e., interactions between unlike molecules are dierent from those between like molecules. For a binary "regular mixture", the Hildebrand-Scatchard theory gives the activity coecients as14 e RT ln 1 = V1L 2 ( 1 2 )2 2 e RT ln 2 = V2L 2 ( 1 2 )2 1 and 2 = (8.5-2) (8.5-3) (8.4-31)

The terms 1 and 2 represent the volume fractions of components 1 and 2, respectively: 1 = e x1 V1L e x2 V2L (8.5-4)

The terms 1 and 2 represent solubility parameters and their values are given by Barton (1975, 1991). As shown in Problem 8.23, solubility parameters can be estimated by using the following formula: v u e vap u Hi RT (8.5-5) i = t e ViL

13 14

eL e x1 V1 + x2 V2L

eL e x1 V1 + x2 V2L

It takes into account the nonrandom distribution of molecules of "1" around a molecule of "2". See Problem 8.23 for the development of Eqs. (8.5-2) and (8.5-3).

240

It follows from Eqs. (8.5-2), (8.5-3), and (8.5-5) that only pure component experimental data (liquid density, vapor pressure, and enthalpy of vaporization) are sucient to estimate activity coecients. Solubility parameters of various liquids are given in Table 8.115 . The smaller the dierence in solubility parameters, the higher the solubility of substances in each other. For example, solubility parameters of water and toluene are very dierent from each other. As a result, solubility of water in toluene is very low. When solubility parameters are equal to each other, e Eq. (11) of Problem 8.23 gives Gex = 0, implying ideal mixture behavior, i.e., i = 1. Table 8.1 Molar liquid volumes and solubility parameters for various solvents at 298 K. Solvent Benzene Carbon tetrachloride Cyclohexane Ethyl benzene n-Hexane n-Octane n-Pentane Toluene Water e VL 3 / mol) ( cm 89 97 109 123 132 164 116 107 18 ( J/ cm3 )1/2 18.7 18.0 16.8 18.0 14.9 15.3 14.4 18.3 48.0

The squared terms on the right-hand sides of Eqs. (8.5-2) and (8.5-3) imply that ln i > 0 i > 1 (8.5-6)

Therefore, the regular mixture theory is not able to predict the negative deviations from Raoults law, i.e., i < 1. Moreover, at constant composition, the right-hand sides of Eqs. (8.5-2) and (8.5-3) are constant. Thus, ln i is proportional to 1/T . In the case of insucient experimental data, such a relationship can be used to estimate the variation in activity coecient with temperature at constant composition. If the parameters A and B in the van Laar equations are dened as A= e V1L ( 1 2 )2 and B= e V2L ( 1 2 )2 (8.5-7)

RT

RT

then Eqs. (8.4-13) and (8.4-14) reduce to Eqs. (8.5-2) and (8.5-3), respectively. Example 8.10 A binary liquid mixture consists of 40 mol % n-pentane (1) and 60% benzene (2). Calculate the activity coecients at 318 K by using the regular mixture theory. Solution From Table 8.1 e V1L = 116 cm3 / mol and and e V2L = 89 cm3 / mol

15

Traditionally, solubility parameters are reported in ( cal/ cm3 )1/2 . Note that ( cal/ cm3 )1/2 ' 2.045 ( J/ cm3 )1/2

241

The volume fractions of n-pentane and benzene are calculated from Eq. (8.5-4) as 1 = 2 = (0.4)(116) = 0.465 (0.4)(116) + (0.6)(89) (0.6)(89) = 0.535 (0.4)(116) + (0.6)(89)

The use of Eqs. (8.5-2) and (8.5-3) yields (116)(0.535)2 (14.4 18.7)2 1 = exp = 1.261 (8.314)(318) (89)(0.465)2 (14.4 18.7)2 = 1.144 2 = exp (8.314)(318) Comment: It is implicitly assumed that the liquid volumes are independent of temperature.

In general, predictions of "regular mixture" approximation are good for mixtures of nonpolar molecules. 8.6 UNIFAC If experimental data are unavailable, a group contribution technique such as UNIFAC can be used to estimate activity coecients of nonelectrolytes in a liquid mixture. In the UNIFAC model, the activity coecient is calculated from the sum of the combinatorial activity coecient, C , and the residual activity coecient, R , in the form i i ln i = ln C + ln R i i (8.6-1)

The combinational part, which is dependent on the surface area and volume of each molecule, is calculated from ln C i = ln i xi + 5 qi ln i i + li i X xj lj xi

j

(8.6-2)

in which xi represents the mole fraction of component i and the summations are over all components, including component i. The terms i (volume fraction), i (surface area fraction), and li are dened by ri xi i = P rj xj

j

qi xi i = P qj xj

j

li = 1 ri + 5(ri qi )

(8.6-3)

In Eq. (8.6-3), the molecular volume, ri , and the molecular surface area, qi , are calculated as X (i) X (i) k Rk and qi = k Qk (8.6-4) ri =

k k

where k is the number of k groups present in component i. Values of R and Q for some selected groups and subgroups are given in Table 8.2.

(i)

242

Table 8.2 UNIFAC group volume and surface area parameters for selected groups (Hansen et al., 1991). Group CHx Subgroup CH3 CH2 CH C CH2=CH CH=CH CH2=C CH=C C=C ACH AC OH CH3 OH H2 O ACOH CH3 CO CH2 CO COOH HCOOH CHCl3 CCl3 R 0.9011 0.6744 0.4469 0.2195 1.3454 1.1167 1.1173 0.8886 0.6605 0.5313 0.3652 1.0000 1.4311 0.9200 0.8952 1.6724 1.4457 1.3013 1.5280 2.8700 2.6401 Q 0.848 0.540 0.228 0.000 1.176 0.867 0.988 0.676 0.485 0.400 0.120 1.200 1.432 1.400 0.680 1.488 1.180 1.224 1.532 2.410 2.184 Example n-Pentane = 2 CH3 + 3 CH2 n-Butane = 2 CH3 + 2 CH2 2, 3-Dimethylbutane = 4 CH3 + 2 CH 2, 2, 3, 3-Tetramethylbutane = 2 C + 6 CH3 3-Methyl-1-Hexene = 2 CH3 + 2 CH2 + 1 CH +1 CH2=CH 2-Hexene = 2 CH3 + 2 CH2 + 1 CH=CH 3-Methyl-1-Butene = 2 CH3 + 1 CH +1 CH2=C 2-Methyl-2-Butene = 3 CH3 + 1 CH=C 2, 3-Dimethylbutene = 4 CH3 + 1 C=C Benzene = 6 ACH Styrene = 1CH2=CH +5 ACH +1 AC Ethanol = 1 CH3 + 1 CH2 + 1 OH Methanol = 1 CH3 OH Water = 1 H2 O Phenol = 5 ACH + 1 ACOH Methyl ethyl ketone = 1 CH3 + 1 CH2 + 1CH3 CO Diethyl ketone = 2 CH3 + 1 CH2 + 1 CH2 CO Acetic acid = 1CH3 + 1 COOH Formic acid = 1 HCOOH Chloroform = 1CHCl3 1,1,1-Trichloroethane = 1CH3 + 1 CCl3

C=C

1

The residual part of the activity coecient describes the intermolecular forces and is calculated from i X (i) h (i) ln R = k ln k ln k (8.6-5) i

k

where k is the contribution of functional group k to the residual activity coecient, and k is the contribution of group k in the pure uid i at the same temperature and pressure as the (i) mixture. The term k is needed in Eq. (8.6-5) to satisfy the condition that i 1 as xi 1. These quantities are calculated by the following expression: ! X X m km (i) P ln k (or ln k ) = Qk 1 ln m mk (8.6-6) n nm m m

n

(i)

where the summations are over all dierent groups. The area fraction of group m, m , is dened by Qm Xm m = P (8.6-7) Qn Xn

n

243

j

m xj n xj

(j)

(j)

in which amn 6= anm . Table 8.3 gives values of amn for interactions between six representative main groups. Table 8.3 UNIFAC group-group interaction parameters for selected groups (Poling et al., 2004). amn ( K) m CHx C=C ACH OH H2 O CH2 CO n CHx 0.0 35.36 11.12 156.4 300 26.76 C=C 86.02 0.0 3.446 457.0 496.1 42.92 ACH 61.13 38.81 0.0 89.60 362.3 140.1 OH 986.5 524.1 636.1 0.0 229.1 164.5 H2 O 1318 270.6 903.8 353.5 0.0 472.5 CH2 CO 476.4 182.6 25.77 84.00 195.4 0.0

Xm = P P

j n

(8.6-8)

(8.6-9)

Example 8.11 Estimate the activity coecients of a binary liquid consisting of 73 mole % acetone (1) and 27% benzene (2) at 332.4 K. Solution While acetone has one CH3 group and one CH3 CO group, benzene has six ACH groups. From Table 8.2 Acetone (i = 1): 1 CH3 (k = A) 1 CH3 CO (k = B) Benzene (i = 2): 6 ACH (k = C) Thus, k values are

(i)

(2)

(1)

B = 1 B = 0

(2)

(1)

C = 0 C = 6

(2)

(1)

The molecular volumes and surface areas are calculated from Eq. (8.6-4) as r1 = (1)(0.9011) + (1)(1.6724) = 2.5735 r2 = (6)(0.5313) = 3.1878 244

q1 = (1)(0.848) + (1)(1.488) = 2.336 q2 = (6)(0.400) = 2.400 The volume and surface area fractions as well as the parameter li are calculated from Eq. (8.6-3) as (2.5735)(0.73) = 0.6858 (2.5735)(0.73) + (3.1878)(0.27) (3.1878)(0.27) = 0.3142 2 = (2.5735)(0.73) + (3.1878)(0.27) 1 = 1 = (2.336)(0.73) = 0.7246 (2.336)(0.73) + (2.400)(0.27) (2.400)(0.27) = 0.2754 2 = (2.336)(0.73) + (2.400)(0.27)

l1 = 1 2.5735 + (5)(2.5735 2.336) = 0.3860 l2 = 1 3.1878 + (5)(3.1878 2.400) = 1.7512 Thus, the combinatorial part of the activity coecients is calculated from Eq. (8.6-2) as 0.7246 0.6858 C + (5)(2.336) ln 0.3860 ln 1 = ln 0.73 0.6858 i 0.6858 h (0.73)( 0.386) + (0.27)(1.7512) = 0.01486 0.73 ln C 2 = ln 0.3142 0.27 0.2754 + (5)(2.400) ln + 1.7512 0.3142 i 0.3142 h (0.73)( 0.386) + (0.27)(1.7512) = 0.09883 0.27

Interaction parameters should be considered between the main groups. The subgroups CH3 ( k = A), CH3 CO ( k = B), and ACH ( k = C) belong to CHx , CH2 CO, and ACH main groups, respectively. Hence, from Table 8.3 aAA = 0 aBA = 26.76 aCA = 11.12 From Eq. (8.6-9) AA = 1 BA = 0.9226 CA = 1.0340 AB = 0.2385 BB = 1 CB = 0.9254 AC = 0.8320 BC = 0.6561 CC = 1 aAB = 476.4 aBB = 0 aCB = 25.77 aAC = 61.13 aBC = 140.1 aCC = 0

For pure acetone ( i = 1), the mole fractions of groups CH3 and CH3 CO are

(1) XA

A

(1) A

(1)

(1) + B

and

XB = 0.5

(1)

The group area fractions in pure acetone are calculated from Eq. (8.6-7) as A = B =

(1) (1)

Contributions of groups CH3 and CH3 CO in pure acetone are calculated from Eq. (8.6-6) as

(1) ln A

= 0.848

(1) ln B

= 1.488

(2)

Since only one main group exists in benzene ln C = 0 Now, contributions of the functional groups to the residual activity coecient, k , should be calculated. The use of Eq. (8.6-8) gives the group mole fractions in solution as A x1 + A x2 (1)(0.73) = 0.237 = XA = h h i i (2)(0.73) + (6)(0.27) (1) (1) (1) (2) (2) (2) A + B + C x1 + A + B + C x2 XB = XC = (1)(0.73) = 0.237 (2)(0.73) + (6)(0.27) (6)(0.27) = 0.526 (2)(0.73) + (6)(0.27)

(1) (2)

The volume fractions are calculated from Eq. (8.6-7) as A = B = C = QA XA (0.848)(0.237) = 0.263 = QA XA + QB XB + QC XC (0.848)(0.237) + (1.488)(0.237) + (0.400)(0.526) (1.488)(0.237) = 0.462 (0.848)(0.237) + (1.488)(0.237) + (0.400)(0.526) (0.400)(0.526) = 0.275 (0.848)(0.237) + (1.488)(0.237) + (0.400)(0.526)

246

ln A = 0.848

h i 1 ln (0.263)(1) + (0.462)(0.9226) + (0.275)(1.0340) (0.263)(1) (0.263)(1) + (0.462)(0.9226) + (0.275)(1.0340) (0.462)(0.2385) + (0.263)(0.2385) + (0.263)(1) + (0.275)(0.9254) (0.275)(0.8320) = 0.1894 + (0.263)(0.8320) + (0.263)(0.6561) + (0.275)(1) ln B = 0.2692 ln C = 0.0216

Similarly,

From Eq. (8.6-5) ln R = (1)(0.1894 0.389) + (1)(0.2692 0.135) = 0.0654 1 Activity coecients can be calculated from Eq. (8.6-1) as ln 1 = 0.01486 0.0654 = 0.05054 ln 2 = 0.09883 + 0.1296 = 0.22843 ln R = (6)(0.0216 0) = 0.1296 2 = =

1 = 0.951 2 = 1.257

8.7 INFINITE DILUTION ACTIVITY COEFFICIENTS The use of the activity coecient models discussed in Section 8.4 requires the parameters to be known. The parameters appearing in these models, on the other hand, are closely related to the innite-dilution activity coecients as shown in Table 8.4. Once the innite-dilution activity coecients are known, then parameters can be easily determined. Moreover, the design of processes involving the separation of dilute contaminants (or hazardous substances) from water and/or a waste stream requires the innite dilution activity coecient to be known. Sherman et al. (1996) summarized various direct and indirect experimental measurement methods for the estimation of innite-dilution activity coecients. On the other hand, the values of activity coecients at innite dilution are tabulated by Tiegs et al. (1986). Once the experimental VLE data are obtained, innite-dilution activity coecients can be estimated as follows: The use of Eq. (8.3-13) gives the activity coecients as a function of composition. Then extrapolation of the experimental data to innite dilution, i.e., xi 0, gives innite-dilution activity coecients, . i Extrapolation to innite dilution can be carried out by using various techniques, one of which is the Lagrange three-point formula. The Lagrange interpolating polynomial is the polynomial of degree n 1 that passes through n points y1 = f (x1 ), y2 = f (x2 ), ..., yn = f (xn ). It is given by n X Pj (x) (8.7-1) P (x) =

j=1

where

Pj (x) = yj

n Q x xk k=1 xj xk k6=j

(8.7-2)

247

Table 8.4 Innite dilution activity coecients for various models. Model Two-Sux Margules Three-Sux Margules Innite Dilution Activity Coecients = = exp A 1 2 = exp(A B) 1 = exp(A + B) 2 = exp A 1 = exp B 2 = exp ( ln 12 + 1 21 ) 1

van Laar

Wilson

NRTL

= exp ( ln 21 + 1 12 ) 2

Hildebrand-Scatchard = exp 2

RT

For n = 3, substitution of Eq. (8.7-2) into Eq. (8.7-1) leads to (x x2 )(x x3 ) (x x1 )(x x3 ) (x x1 )(x x2 ) + y2 + y3 (8.7-3) P (x) = y1 (x1 x2 )(x1 x3 ) (x2 x1 )(x2 x3 ) (x3 x1 )(x3 x2 ) When x = 0, Eq. (8.7-3) reduces to x2 x3 x1 x3 x1 x2 P (0) = y1 + y2 + y3 (8.7-4) (x1 x2 )(x1 x3 ) (x2 x1 )(x2 x3 ) (x3 x1 )(x3 x2 ) Therefore, innite-dilution activity coecients are calculated as x1 x1 1 x1 x1 1 x1 x1 1 =h ih i+h ih i+h ih i (1) (2) (1) (3) (2) (1) (2) (3) (3) (1) (3) (2) x1 x1 x1 x1 x1 x1 x1 x1 x1 x1 x1 x1 x2 x2 2 x2 x2 2 x2 x2 2 =h ih i+h ih i+h ih i (1) (2) (1) (3) (2) (1) (2) (3) (3) (1) (3) (2) x2 x2 x2 x2 x2 x2 x2 x2 x2 x2 x2 x2

(2) (3) (1) (1) (3) (2) (1) (2) (3) (2) (3) (1) (1) (3) (2) (1) (2) (3)

(8.7-5)

(8.7-6)

248

Example 8.12 Alonso et al. (2004) reported the following isothermal VLE data for a binary mixture of methanol (1) and n-hexane (2) at 313.15 K: a) Determine the innite-dilution activity coecients by using the Lagrange three-point formula. b) Determine the parameters in the Wilson equation and estimate the vapor phase composition for the given x1 values. P ( kPa) 37.313 61.555 64.676 66.110 67.822 68.539 68.664 68.759 68.831 68.878 68.912 Solution a) It is rst necessary to calculate the activity coecients from Eq. (8.3-13), i.e., 1 = y1 P

vap x1 P1

x1 0.0000 0.0386 0.0544 0.0667 0.1027 0.1856 0.2050 0.2273 0.2524 0.2770 0.3008

y1 0.0000 0.4060 0.4390 0.4530 0.4698 0.4768 0.4779 0.4794 0.4811 0.4826 0.4839

P ( kPa) 68.943 68.948 68.967 68.960 68.969 68.962 68.960 68.948 68.927 68.902 68.850

x1 0.3449 0.4065 0.4163 0.5004 0.5008 0.5987 0.6043 0.6517 0.7008 0.7256 0.7516

y1 0.4848 0.4849 0.4848 0.4821 0.4821 0.4795 0.4795 0.4796 0.4800 0.4810 0.4824

P ( kPa) 68.748 68.616 68.353 67.935 67.284 66.016 63.747 59.703 50.569 35.464

x1 0.7757 0.7986 0.8259 0.8489 0.8711 0.8968 0.9224 0.9472 0.9757 1.0000

y1 0.4840 0.4859 0.4890 0.4931 0.4992 0.5112 0.5336 0.5764 0.6925 1.0000

and

2 =

y2 P x2 P2

vap

(1)

For example, let us calculate 1 and 2 values for the following data set: P ( kPa) 68.759 x1 0.2273 y1 0.4794

vap vap From the given data, P1 = 35.464 kPa and P2 = 37.313 kPa at 313.15 K. The activity coecients are y1 P (0.4794)(68.759) = = 4.089 1 = vap (0.2273)(35.464) x1 P1

2 =

y2 P

vap x2 P2

The calculated values of the activity coecients as a function of composition are given in the table below:

249

x1 0.0386 0.0544 0.0667 0.1027 0.1856 0.2050 0.2273 0.2524 0.2770 0.3008

1 18.256 14.717 12.661 8.748 4.965 4.514 4.089 3.699 3.384 3.126

2 1.019 1.028 1.038 1.074 1.180 1.209 1.242 1.280 1.321 1.363

x1 0.3449 0.4065 0.4163 0.5004 0.5008 0.5987 0.6043 0.6517 0.7008 0.7256

1 2.733 2.319 2.265 1.873 1.872 1.557 1.543 1.431 1.331 1.288

2 1.453 1.604 1.631 1.916 1.918 2.397 2.431 2.761 3.210 3.493

x1 0.7516 0.7757 0.7986 0.8259 0.8489 0.8711 0.8968 0.9224 0.9472 0.9757

1 1.246 1.210 1.177 1.141 1.113 1.087 1.061 1.040 1.024 1.012

2 3.845 4.239 4.694 5.377 6.108 7.006 8.380 10.268 12.837 17.150

The values of the liquid phase mole fractions and the activity coecients to be used in Eqs. (8.7-5) and (8.7-6) are given below:

i 1 2 3

x1

(i)

(i)

x2

(i)

(i)

Therefore, the innite-dilution activity coecients are calculated as = 1 (0.0386)(0.0667)(14.717) (0.0544)(0.0667)(18.256) + (0.0386 0.0544)(0.0386 0.0667) (0.0544 0.0386)(0.0544 0.0667) (0.0386)(0.0544)(12.661) = 31.149 + (0.0667 0.0386)(0.0667 0.0544) (0.0243)(0.0776)(12.837) (0.0528)(0.0776)(17.150) + (0.0243 0.0528)(0.0243 0.0776) (0.0528 0.0243)(0.0528 0.0776) (0.0243)(0.0528)(10.268) = 21.977 + (0.0776 0.0243)(0.0776 0.0528)

= 2

b) The use of Eq. (8.4-24) gives 1 1 12 = exp 1 exp (1 12 ) 31.149 21.977 The parameter 21 can be estimated from Eq. (8.4-25) as

12 = 0.078

21 = 1 ln [(0.078)(31.149)] = 0.112 Once 1 values are calculated from Eq. (8.4-19) at each x1 value, the gas phase composition is determined from vap 1 x1 P1 calc y1 = P and the results are tabulated below: 250

x1 0.0386 0.0544 0.0667 0.1027 0.1856 0.2050 0.2273 0.2524 0.2770 0.3008

1 15.239 12.413 10.810 7.775 4.644 4.237 3.848 3.486 3.191 2.949

exp y1

calc y1

x1 0.3449 0.4065 0.4163 0.5004 0.5008 0.5987 0.6043 0.6517 0.7008 0.7256

1 2.585 2.205 2.154 1.802 1.801 1.516 1.502 1.398 1.305 1.264

exp y1

calc y1

x1 0.7516 0.7757 0.7986 0.8259 0.8489 0.8711 0.8968 0.9224 0.9472 0.9757

1 1.223 1.189 1.159 1.125 1.100 1.077 1.054 1.033 1.017 1.004

exp y1

calc y1

0.4060 0.4390 0.4530 0.4698 0.4768 0.4779 0.4794 0.4811 0.4826 0.4839

0.3389 0.3703 0.3868 0.4176 0.4460 0.4486 0.4511 0.4533 0.4550 0.4564

0.4848 0.4849 0.4848 0.4821 0.4821 0.4795 0.4795 0.4796 0.4800 0.4810

0.4586 0.4609 0.4612 0.4637 0.4637 0.4666 0.4668 0.4685 0.4706 0.4719

0.4824 0.4840 0.4859 0.4890 0.4931 0.4992 0.5112 0.5336 0.5764 0.6925

0.4736 0.4757 0.4782 0.4822 0.4873 0.4945 0.5075 0.5302 0.5723 0.6872

An alternative approach for determining innite dilution activity coecients is to use e Redlich-Kister type expansion in expressing Gex /RT as a function of composition, i.e., Eq. (8.3-15). Then it follows from Eqs. (8.3-21) and (8.3-22) that ln 1

n X = ( 1)i1 Ai i=1

and

ln 2

n X i=1

Ai

(8.7-7)

Example 8.13 Using the data given in Example 8.12, estimate innite dilution activity coecients using Eq. (8.7-7). Solution e The term Gex /RT can be determined from Eq. (8.3-10), i.e., The calculated values are given below: x1 0.0386 0.0544 0.0667 0.1027 0.1856 0.2050 0.2273 0.2524 0.2770 0.3008 e Gex /RT 0.117 0.159 0.188 0.266 0.405 0.430 0.457 0.485 0.508 0.529 e Gex = x1 ln 1 + x2 ln 2 RT

(1)

x1 0.3449 0.4065 0.4163 0.5004 0.5008 0.5987 0.6043 0.6517 0.7008 0.7256

e Gex /RT 0.559 0.588 0.591 0.603 0.602 0.581 0.579 0.554 0.518 0.495

x1 0.7516 0.7757 0.7986 0.8259 0.8489 0.8711 0.8968 0.9224 0.9472 0.9757

e Gex /RT 0.469 0.442 0.413 0.375 0.339 0.302 0.254 0.201 0.144 0.071

5 X e Gex = x1 x2 Ai (x1 x2 )i1 RT i=1

251

with A1 = 2.415, A2 = 0.039, A3 = 0.388, A4 = 0.091, and A5 = 0.414. The use of Eq. (8.7-7) gives the innite dilution activity coecients as ln = 2.415 + 0.039 + 0.388 + 0.091 + 0.414 = 3.347 1 ln = 2.415 0.039 + 0.388 0.091 + 0.414 = 3.087 2 = 28.417 1 = 21.911 2

8.8 TESTING CONSISTENCY OF EXPERIMENTAL DATA On a molar basis, Eq. (8.3-17) becomes ! k X e e e V ex H ex Gex = dP d dT + ln i dxi RT RT RT 2

i=1

(8.8-1)

Substitution of Eq. (8.3-10) into the left-hand side of Eq. (8.8-1) and rearrangement give

k X i=1

xi d ln i =

e e H ex V ex dP dT RT RT 2

(8.8-2)

which is known as the Gibbs-Duhem equation for excess properties. In the case of constant temperature and pressure, Eq. (8.8-2) takes the form

k X i=1

xi d ln i = 0

constant T and P

(8.8-3)

For a binary mixture, Eq. (8.8-3) reduces to x1 d ln 1 dx1 + x2 d ln 2 dx1 =0 constant T and P (8.8-4)

Equation (8.8-4) is used to check whether the activity coecients obtained from the experimental data are thermodynamically consistent or not. Example 8.14 In a binary liquid system, the activity coecients of the components are proposed in the form ln 1 = A x1 x2 + x2 1 ln 2 = A x1 x2 + x2 2 Are these equations thermodynamically consistent? Solution The given activity coecient expressions should satisfy the Gibbs-Duhem equation, Eq. (8.8-4), i.e., d ln 1 d ln 2 =0 (1) + x2 x1 dx1 dx1 | {z } d ln 2 dx2 252

The derivatives of the activity coecients are d ln 1 = A + 2 (1 A) x1 dx1 d ln 2 = A + 2 (1 A) x2 dx2 Therefore, the left-hand side of Eq. (1) becomes h i h i d ln 1 d ln 2 x1 x2 = x1 A + 2(1 A)x1 x2 A + 2(1 A)x2 dx1 dx2 = (2 A)(x1 x2 ) (2) (3)

(4)

which is dierent from zero. Therefore, the given equations are thermodynamically inconsistent. Comment: In cases in which the Gibbs-Duhem equation is satised, it is also necessary to check whether i 1 as xi 1. It is important to keep in mind that Eq. (8.8-4) is valid only when both temperature and pressure remain constant. On the other hand, VLE measurements are made at either constant temperature or constant pressure16 . For this purpose, the integrated form of Eq. (8.8-1) is used. For a binary system, Eq. (8.8-1) takes the form ! e e e 1 H ex Gex V ex dP dT + ln (8.8-5) d dx1 = 2 RT RT RT 2 or d dx1 Integration of Eq. e Gex RT x1 =1 | {z

0

or

1

e Gex RT

e e 1 H ex dT V ex dP + ln = 2 dx RT dx1 RT 2 1

(8.8-6)

(8.8-7)

ln

1 2

dx1 =

vap P1

vap P2

Z T sat e ex e 1 V ex H dP + dT sat RT 2 RT T2

(8.8-8)

8.8.1 Isothermal VLE Data When the VLE measurements are made under constant temperature, Eq. (8.8-8) simplies to Z 1 Z P vap e ex 1 1 V dP (8.8-9) dx1 = ln vap 2 RT P2 0

Excess volume (or volume change on mixing) may be considered negligible for most systems. Under these conditions, the right-hand side of Eq. (8.8-9) is almost zero, i.e., Z 1 1 ln (8.8-10) dx1 = 0 2 0

For a binary system, Gibbs phase rule indicates that F = 2. Therefore, when temperature (or pressure) is xed, compositions of the liquid and vapor phases cannot be changed without varying pressure (or temperature).

16

253

Therefore, when the data are plotted in the form of ln( 1 / 2 ) versus x1 , as shown in Figure 8.9, the areas above (P ) and below (N ) the x1 -axis must be equal. In the literature, this is known as the area test of Redlich and Kister (1948).

ln 1 2

P

0

N

x1

Figure 8.9 Area test for the thermodynamic consistency of isothermal VLE data. As a result of errors involved in experiments, it is obvious that Eq. (8.8-8) can never be satised exactly. In the literature, the following criteria are used for consistent data: Z 1 1 A = 100 (8.8-11) dx1 < 3 ln 2 0 or Z D = 100 ln dx1 0 < 10 P + |N |

1

1 2

(8.8-12)

Example 8.15 The following isothermal VLE data are reported by Hiaki et al. (1998) for a binary system of 2-methyl-2-propanol (1) and octane (2) at 343.15 K. Check whether the experimental data are consistent.

x1 0.0834 0.1061 0.1329 0.1610 0.2411 0.2939 0.3591 0.3896 0.4553 0.4872 Solution

1 3.8957 3.4608 3.0925 2.8056 2.2293 1.9356 1.6969 1.6053 1.4540 1.3917

2 1.0297 1.0448 1.0539 1.0626 1.1540 1.1962 1.2765 1.3185 1.4211 1.4831

x1 0.5039 0.5209 0.5598 0.6175 0.6372 0.6756 0.7372 0.7468 0.8083 0.8453

1 1.3684 1.3493 1.2915 1.2184 1.2058 1.1626 1.1084 1.1011 1.0621 1.0435

2 1.5106 1.5339 1.6061 1.7332 1.7932 1.8955 2.1265 2.1688 2.4505 2.6489

x1 0.8537 0.8920 0.9061 0.9285 0.9353 0.9533 0.9608 0.9684 0.9763 0.9839

1 1.0395 1.0228 1.0169 1.0119 1.0106 1.0088 1.0070 1.0063 1.0053 1.0034

2 2.7352 3.0081 3.1844 3.3567 3.4333 3.6277 3.7223 3.8161 3.8714 4.0228

1.5 1.331

Fitting a fth-order polynomial to the data points yields 1 ln = 1.7576 5.6602 x1 + 4.6434 x2 + 0.5137 x3 4.8185 x4 + 2.1238 x5 1 1 1 1 2 Thus, Z 1 1.7576 5.6602 x1 + 4.6434 x2 + 0.5137 x3 4.8185 x4 + 2.1238 x5 dx1 = 6.0083103 1 1 1 1

0

A = (100)(6.0083 103 ) = 0.6 < 3 Note that ln( 1 / 2 ) = 0 when x1 = 0.4659. Therefore, the positive and negative areas are P = Z

0.4659 1

N=

0.4659

1.7576 5.6602 x1 + 4.6434 x2 + 0.5137 x3 4.8185 x4 + 2.1238 x5 dx1 = 0.3556 1 1 1 1 D = 100 6.0083 103 0.3496 + 0.3556 = 0.852 < 10

8.8.2 Isobaric VLE Data When the VLE measurements are carried out under constant pressure, Eq. (8.8-8) simplies to Z 1 Z T sat e ex 1 1 H ln dT (8.8-13) dx1 = sat RT 2 2 0 T2

255

e where hHmix i is the average value of the heat of mixing in the total concentration range. By examining various binary systems, Herington proposed the following empirical criterion for thermodynamic consistency: |D J| < 10 (8.8-15) where D is dened by Eq. (8.8-12) and J is given by Tmax Tmin J = 150 Tmin

Herington (1951) evaluated the right-hand side of Eq. (8.8-13) as follows: Z T sat e ex Z 1/T sat e ex 1 1 1 H H d dT = 2 sat RT sat R T T2 1/T2 e hH ex i 1 1 = sat sat R T1 T2 e hHmix i 1 1 = T sat T sat R

1 2

(8.8-14)

(8.8-16)

in which Tmin and Tmax are the minimum and maximum temperatures (in K) in the range 0 x1 1, respectively. Example 8.16 The following isobaric VLE data are reported by Huang et al. (2004) for a binary system of tetraethyl orthosilicate (1) and ethanol (2) at 24 kPa. Check whether the experimental data are consistent. T ( K) 319.5 319.8 320.3 321.0 321.8 323.1 323.9 325.6 327.0 329.0 331.1 338.5 342.0 Solution The minimum and maximum temperatures are Tmin = 319.5 K The use of Eq. (8.8-16) gives J = 150 393.4 319.5 319.5 256 = 34.7 Tmax = 393.4 K x1 0.0000 0.0430 0.0661 0.1080 0.1623 0.2224 0.3402 0.4322 0.5064 0.5931 0.7131 0.7875 0.8227 1 5.9456 3.9699 2.5875 2.3458 1.8888 1.5448 1.3788 1.3360 1.3287 1.3196 1.3113 1.2878 2 1.0000 1.0239 1.0280 1.0333 1.0525 1.0607 1.1949 1.2712 1.3577 1.4806 1.6928 1.7300 1.7333 T ( K) 350.5 355.8 358.5 366.0 371.7 375.0 376.6 382.0 384.9 387.5 390.7 393.4 x1 0.8875 0.9163 0.9281 0.9534 0.9681 0.9749 0.9782 0.9872 0.9911 0.9942 0.9987 1.0000 1 1.2140 1.1772 1.1395 1.0995 1.0859 1.0575 1.0563 1.0553 1.0436 1.0339 1.0215 1.0000 2 1.7640 1.7894 1.8098 1.8151 1.8210 1.8499 1.8701 1.8758 1.9020 1.9363 3.8249

Fitting a fth-order polynomial to the data points yields 1 ln = 2.413 20.043 x1 + 84.010 x2 182.492 x3 + 186.021 x4 70.733 x5 1 1 1 1 2 Thus, Z

1

Note that ln( 1 / 2 ) = 0 when x1 = 0.499. Therefore, the positive and negative areas are Z 0.499 2.413 20.043 x1 + 84.010 x2 182.492 x3 + 186.021 x4 70.733 x5 dx1 = 0.329 P = 1 1 1 1 N= The use of Eq. (8.8-12) gives Z

0 1 0.499

2.413 20.043 x1 + 84.010 x2 182.492 x3 + 186.021 x4 70.733 x5 dx1 = 0.141 1 1 1 1 D = 100 0.187 0.329 + 0.141 = 39.8

From Eq. (8.8-15) Therefore, the data are consistent. |D J| = 39.8 34.7 = 5.1 < 10

One should keep in mind that even if the data satisfy the aforementioned tests the reliability of experimental data set is still in question. Various other thermodynamic consistency tests are also available in the literature (Wisniak, 1993; Wisniak, 1994; van Ness, 1995). As stated by Prausnitz et al. (1999), "The literature is rich with articles on testing for thermodynamic consistency because it is much easier to test someone elses data than to obtain ones own in the laboratory. Much (but by no means all) of this literature is obscured by excessive use of statistics. It has been said that patriotism is the last refuge of a scoundrel. Similarly, we might say that statistics is the last refuge of a poor experimentalist or, in a more positive way, that a gram of good data is worth more than a ton of consistency tests." 8.9 CONCLUDING REMARKS As will be shown in the following chapters, calculation of activity coecients is of critical importance in the design of separation equipment. The activity coecient models mentioned in Sections 8.4, 8.5, and 8.6 are not the only ones available in the literature. Since there is no universal equation that can represent all types of liquid mixtures, there is an abundance of activity coecient models. This brings up the question of how to choose the "best" activity coecient model for a given system. Furthermore, the aferomentioned models are all limited to binary mixtures. How one can calculate the activity coecients for multicomponent mixtures? 8.9.1 Which Activity Coecient Model to Use? Simulation packages given in Appendix H provide guidelines in choosing the appropriate activity coecient model. For moderately nonideal and polar solutions, the NRTL, Wilson, and van Laar models can be used. When the system is highly nonideal and polar, the NRTL model is preferred. For more details on the subject, the reader should refer to Carlson (1996), Zygula et al. (2001), Chen and Mathias (2002), Suppes (2002), and Poling et al. (2004). 257

8.9.2 Activity Coecients for Multicomponent Mixtures Most of the published data related to vapor-liquid, liquid-liquid, and solid-liquid equilibria are for binary systems. In that respect, eorts have been directed to extend available binary models to multicomponent systems so that the resulting equations require only the data for the binary subsystems. For example, the Wilson model for a multicomponent system is given by k k X X mi xm ln i = 1 ln ij xj (8.9-1) P k m=1 j=1 mj xj

j=1

where ij = 1 for i = j. In the case of a ternary system, Eq. (8.9-1) takes the form ln i = 1 ln (i1 x1 + i2 x2 + i3 x3 )

1i x1 2i x2 x1 + 12 x2 + 13 x3 21 x1 + x2 + 23 x3 3i x3 31 x1 + 32 x2 + x3

(8.9-2)

Example 8.17 Kirss et al. (2005) reported the following binary Wilson parameters as a function of temperature: 728.735 155.701 21 = exp 1.03432 + 12 = exp 1.70016 T T 839.958 195.303 13 = exp 2.17687 31 = exp 0.86126 + T T 314.903 1774.377 32 = exp 3.58544 23 = exp 0.05676 T T where 1, 2, and 3 represent methylbutyl ketone, nonane, and cyclohexanol, respectively. For a ternary system, the experimental data at 408.88 K and 80 kPa indicate the liquid phase composition as x2 = 0.256 x3 = 0.616 x1 = 0.128 a) Determine the activity coecients in a ternary mixture of methylbutyl ketone, nonane, and cyclohexanol. b) Estimate the vapor phase composition in equilibrium with the liquid. Data: The vapor pressures of the components are given by

vap ln P1 = 14.005

Solution a) At 408.88 K, the binary Wilson parameters are 12 = 0.921 13 = 1.130 23 = 0.490 21 = 0.520 31 = 0.681 32 = 0.470

Substitution of the numerical values into Eq. (8.9-2) gives the activity coecients as 1 = exp h i 1 ln 0.128 + (0.921)(0.256) + (1.130)(0.616)

(0.520)(0.256) 0.128 0.128 + (0.921)(0.256) + (1.130)(0.616) (0.520)(0.128) + 0.256 + (0.490)(0.616) (0.681)(0.616) = 1.104 (0.681)(0.128) + (0.470)(0.256) + 0.616 h i 1 ln (0.520)(0.128) + 0.256 + (0.490)(0.616)

2 = exp

0.256 (0.921)(0.128) 0.128 + (0.921)(0.256) + (1.130)(0.616) (0.520)(0.128) + 0.256 + (0.490)(0.616) (0.470)(0.616) = 1.819 (0.681)(0.128) + (0.470)(0.256) + 0.616 h i 1 ln (0.681)(0.128) + (0.470)(0.256) + 0.616

3 = exp

(0.490)(0.256) (1.130)(0.128) 0.128 + (0.921)(0.256) + (1.130)(0.616) (0.520)(0.128) + 0.256 + (0.490)(0.616) 0.616 = 1.115 (0.681)(0.128) + (0.470)(0.256) + 0.616

vap P1 = 127.116 kPa vap P2 = 66.758 kPa vap P3 = 44.961 kPa

vap 1 x1 P1

P

vap 2 x2 P2

P vap 3 x3 P3 P

= =

259

REFERENCES Abrams, D.S. and J.M. Prausnitz, 1975, AIChE Journal, 21 (1), 116-128. Alonso, C., E.A. Montero, C.R. Chamorro, J.J. Segovia, M.C. Martin and M.A. Villamanan, 2004, Fluid Phase Equilibria, 217, 157-164. Barton, A.F.M., 1975, Chem. Rev., 75 (6), 731-753. Barton, A.F.M., 1991, Handbook of Solubility Parameters and Other Cohesion Parameters, 2nd Ed., CRC Press, Boca Raton. Black, C., 1958, Ind. Eng. Chem., 50, 403-412. Campbell, S.W., R.A. Wilsak and G. Thodos, 1987, J. Chem. Eng. Data, 32, 357-362. Carley, J.F. and L.W. Bertelsen, 1949, Ind. Eng. Chem., 41 (12), 2806-2808. Carlson, E.C., 1996, Chemical Engineering Progress, 92 (10), 35-46. Chen, C.C. and P.M. Mathias, 2002, AIChE Journal, 48 (2), 194-200. Choi, P.B. and E. McLaughlin, 1983, Ind. Eng. Chem. Fundam., 22, 46-51. Constantinescu, D. and I. Wichterle, 2002, Fluid Phase Equilibria, 203, 71-82. Davollo, F., G.C. Pedrosa and M. Katz, 1981, J. Chem. Eng. Data, 26, 26-27. Fenclova, D., P. Vrbka, V. Dohnal, K. Rehak and G.G. Miaja, 2002, J. Chem. Thermodynamics, 34, 361-376. Fredenslund, A., R.L. Jones and J.M. Prausnitz, 1975, AIChE Journal, 21 (6), 1086-1099. Gabaldon, C., P. Marzal, J. Monton and M.A. Rodrigo, 1996, J. Chem. Eng. Data, 41, 1176-1180. Hansen, R.S. and F.A. Miller, 1954, J. Phys. Chem., 58 (3), 193-196. Hansen, H.K., P. Rasmussen, A. Fredenslund, M. Schiller and J. Gmehling, 1991, Ind. Eng. Chem. Res., 30 (10), 2352-2355. Herington, E.F.G., 1951, J. Inst. Pet., 37, 457-470. Hiaki, T., A. Taniguchi, T. Tsuji and M. Hongo, 1998, Fluid Phase Equilibria, 144, 145-155. Kirss, H., M. Kuus and E. Siimer, 2005, J. Chem. Eng. Data, 50, 309-311. Kojima, K. and K. Tochigi, 1979, Prediction of Vapor-Liquid Equilibria by the ASOG Method, Elsevier, Englewood Clis. Kundu, M. and S.S. Bandyopadhyay, 2007, Chem. Eng. Comm., 194, 1138-1159.

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Kyyny, P.U., J.P. Pokki, J. Aittamaa and S. Liukkonen, 2001, J. Chem. Eng. Data, 46, 686-691. Lien, P.J., H.M. Lin and M.J. Lee, 2004, Fluid Phase Equilibria, 215, 187-193. Lozano, L.M., E.A. Montero, M.C. Martin and M.A. Villamanan, 1997, Fluid Phase Equilibria, 133, 155-162. Mara, K., V.R. Bhethanabotla and S.W. Campbell, 1997, Fluid Phase Equilibria, 127, 147-153. Merzougui,A., A. Hasseine, A. Kabouche and M. Korichi, 2011, Fluid Phase Equilibria, 309, 161-167. Mirmehrabi, M., S. Rohani and L. Perry, 2006, J. Pharm. Sciences, 95 (4), 790-797. Mundhwa, M. and A. Henni, 2007, J. Chem. Thermodynamics, 39, 1439-1451. Pemberton, R.C. and C.J. Mash, 1978, J. Chem. Thermodynamics, 10 (9), 867-888. Prasad, T.E.V., N. Venkanna, Y.N. Kumar, K. Ashok, N.M. Sirisha and D.H.L. Prasad, 2007, J. Chem. Thermodynamics, 39, 1022-1026. Poling B.E., J.M. Prausnitz and J.P. OConnell, 2004, The Properties of Gases and Liquids, 5th Ed., Chapter 8, McGraw-Hill, New York. Prausnitz, J.M., R.N. Lichtenthaler and E.G.D. Azevedo, 1999, Molecular Thermodynamics of Fluid-Phase Equilibria, Third Ed., Prentice-Hall. Redlich, O., and A.T. Kister, 1948, Ind. Eng. Chem., 40, 345-348. Renon, H. and J.M. Prausnitz, 1968, AIChE Journal, 14 (1), 135-144. Russinyol, M.D.C.S., A. Auceho and S. Loras, 2004, J. Chem. Eng. Data, 49, 1258-1262. Sapei, E., A. Zaytseva, P.U. Kyyny, K.I. Keskinen and J. Aittamaa, 2006, J. Chem. Eng. Data, 51 (6), 2203-2208. Shacham, M., J. Wisniak and N. Brauner, 1993, Ind. Eng. Chem. Res., 32, 2820-2825. Sherman, S.R., D.B. Trampe, D.M. Bush, M. Schiller, C.A. Eckert, A.J. Dallas, J. Li and P.W. Carr, 1996, Ind. Eng. Chem. Res., 35, 1044-1058. Spencer, C.F. and R.P. Danner, 1972, J. Chem. Eng. Data, 17, 236-241. Suppes, G.J., 2002, Selecting Thermodynamic Models for Process Simulation of Organic VLE and LLE Systems, (http://web.missouri.edu/~suppesg/2002Paper8.htm). Tiegs, D., J. Gmehling, P. Rasmussen and Aa. Fredenslund, 1987, Ind. Eng. Chem. Res., 26, 159-161. Twu, C.H. and J.E. Coon, 1995, Chem. Eng. Prog., 91 (12), 46-53. Van Ness, H.C., 1995, Pure and Applied Chemistry, 67, 859-872. 261

Villamanan, R.M., M.C. Martin, C.R. Chamorro, M.A. Villamanan and J. Segovia, 2006, J. Chem. Thermodynamics, 38, 547-553. Weidlich, U. and J.A. Gmehling, 1987, Ind. Eng. Chem. Res., 26, 1372-1381. Wilson, G.M., 1964, J. Am. Chem. Soc., 86, 127-133. Wisniak, J., 1993, Ind. Eng. Chem. Res., 32, 1531-1533. Wisniak, J., 1994, Ind. Eng. Chem. Res., 33, 177-180. Zarei, H.A. and H. Iloukhani, 2003, Thermochimica Acta, 405, 123-128. Zygula, T.M., E. Roy and P.C. Dautenhahn, 2001, The Importance of Thermodynamics on Process Simulation Packages, AIChE Spring National Meeting, Houston, Texas, (http://kolmetz.com/pdf/Thermo-Paper.pdf ).

PROBLEMS Problem related to Section 8.1 8.1 A beaker contains 20 mol of pure water at 298 K. Calculate the change in Gibbs energy when 0.05 mol of solid X is dissolved in water under isothermal conditions. Assume that the e mixture behaves as an ideal mixture and GX = 300 J/ mol. (Answer: 851.2 J) Problems related to Section 8.2 8.2 A binary liquid mixture of components 1 and 2 is to be heated at constant pressure from T1 to T2 . The molar excess Gibbs energy of the mixture is represented by e Gex = A x1 x2 A=+ T

where

Under isobaric conditions, show that the change in molar entropy of the system is given by ! T2 1 1 e e e 2 Ssys (T2 , P ) Ssys (T1 , P ) = CPmix ln + x1 x2 2 T1 T2 T1 e e e CPmix = x1 CP1 + x2 CP2

8.3 A stream of liquid 1 at 300 K with a ow rate of 2 mol/ s and a stream of liquid 2 at 340 K with a ow rate of 3 mol/ s are mixed in an adiabatic mixer in a steady ow process. The molar excess Gibbs energy of the mixture is represented by e Gex = 1500 x1 x2 262

a) Estimate the temperature of the stream exiting the mixture if the heat capacities for pure components 1 and 2 are 40 J/ mol. K and 60 J/ mol. K, respectively. b) Determine the rate of entropy change as a result of the mixing process. (Answer: a) 320.8 K b) 22.9 W/ K) 8.4 Excess molar heat capacity at constant pressure is dened by ! ! e e H ex S ex eex =T CP = T T

P,xj P,xj

(1)

a) Show that the substitution of Eq. (8.2-19) into Eq. (1) gives ! e 2 Gex ex e CP = T T 2

P,xj

(2)

eex b) If CP is represented by

= a + bT + cT2 (3) R then show that, at constant pressure and composition, molar excess enthalpy and molar excess Gibbs energy are expressed as e b c H ex = a T + T 2 + T 3 + I1 R 2 3 and e I1 b c Gex = a ln T T T 2 + + I2 RT 2 6 T (4)

eex CP

8.5 For a binary mixture of ethanol (1) and cyclohexane (2), the following heat of mixing data are reported by Lien et al. (2004) at 348.15 K: e Hmix ( J/ mol) 704 840 941 1036 1110 1167 1205 1222 1224 e Hmix ( J/ mol) 1198 1147 1076 978 858 717 559 391 226

5 X i=1

Ai (x1 x2 )i1

(1)

and show that A1 = 4925, A2 = 327, A3 = 550, A4 = 2643, and A5 = 3608. 263

b) Use Eq. (6.3-15) and show that the partial molar excess enthalpy of components 1 and 2 are given in the form

ex H1

x2 2

5 X i=1 5 X i=1

Ai (x1 x2 )

i1

+ 2 x1 x2 2

4 X i=1 4 X i=1

(2)

H 2 = x2 1

ex ex

ex

Ai (x1 x2 )i1 2 x2 x2 1

(3)

ex, 5 X ( 1)i1 Ai ex ex, 5 X i=1

and

H2

Ai

(4)

, H 2 = 1614 J/ mol d) H 1

ex,

ex,

5013 J/ mol) 8.6 Fenclova et al. (2002) reported the following data for a binary system of trichloromethane e (1) and tetrahydropyran (2) at 333.15 K. Plot Gex /RT versus x1 and evaluate the activity coecients at x1 = 0.4 graphically. x1 0.0000 0.0298 0.0736 0.1363 0.2150 0.3149 (Answer: 1 = 0.63 e Gex ( J/ mol) 0 83.1 203.0 357.6 525.2 685.5 x1 0.4242 0.5308 0.6244 0.6825 0.6903 0.7101 e Gex ( J/ mol) 788.0 814.6 769.5 720.2 703.3 669.7 x1 0.7631 0.8453 0.9458 0.9767 1.0000 e Gex ( J/ mol) 593.3 425.2 161.5 69.0 0

2 = 0.85)

8.7 For a ternary system represented by the two-sux Margules model, the molar excess Gibbs energy is expressed as e Gex = A12 x1 x2 + A13 x1 x3 + A23 x2 x3 RT

Use Eq. (8.3-18) and show that the activity coecients are given by ln 1 = A12 x2 + A13 x2 + (A12 + A13 A23 ) x2 x3 2 3 ln 2 = A12 x2 + A23 x2 + (A12 + A23 A13 ) x1 x3 1 3 ln 3 = A13 x2 + A23 x2 + (A13 + A23 A12 ) x1 x2 1 2 8.8 For a binary system of components 1 and 2, the molar excess Gibbs energy is expressed as e Gex = x1 x2 (Ax2 + Bx1 Dx1 x2 ) RT 264

Show that the activity coecients are expressed as h i ln 1 = x2 A + 2 (B A D) x1 + 3Dx2 2 1 h i ln 2 = x2 B + 2 (A B D) x2 + 3Dx2 1 2 8.9 Consider the separation of a multicomponent mixture as shown in the gure below:

D (mol/h) xi,D F (mol/h) xi,F xi,B B (mol/h)

b) Show that the minimum work required for the complete separation of an equimolar ideal binary mixture into its pure components at constant temperature and pressure is given by W = 0.693 RT F

a) Show that the minimum amount of work required for this separation process taking place at constant temperature and pressure is given by " # k k k X DX W BX = RT xi,D ln(xi,D i,D ) + xi,B ln(xi,B i,B ) xi,F ln(xi,F i,F ) F F F

i=1 i=1 i=1

8.10 In the development of Eq. (8.3-13), all nonidealities associated with the vapor phase are neglected and the Poynting correction factor is considered unity. Consider a binary mixture and assume that the vapor phase nonidealities are represented by the virial equation of state. a) Show that Eq. (8.3-12) takes the form " # vap 2 e (B11 V1L )(P P1 ) + y2 (2B12 B11 B22 ) P y1 P exp 1 = vap RT x1 P1 " # vap 2 e (B22 V2L )(P P2 ) + y1 (2B12 B11 B22 ) P y2 P exp 2 = vap RT x2 P2

(1)

(2)

b) For a binary mixture of p-dioxane (1) and acetonitrile (2), the following isothermal VLE data are reported by Davollo et al. (1981) at 298.15 K: x1 0.0000 0.1125 0.2000 0.3070 0.4005 y1 0.0000 0.0640 0.1125 0.1715 0.2272 P ( kPa) 11.87 11.33 10.90 10.30 9.81 x1 0.5170 0.5506 0.6470 0.7465 0.8130 y1 0.3002 0.3235 0.4013 0.4971 0.5812 P ( kPa) 9.14 8.91 8.27 7.52 6.94 x1 0.8988 0.9300 1.0000 y1 0.7262 0.7965 1.0000 P ( kPa) 6.05 5.69 4.83

265

With the help of the following data e V1L = 85.78 cm3 / mol e V2L = 52.85 cm3 / mol

calculate the activity coecients using Eqs. (1) and (2). c) Fit the data to the following equation

4 X e Gex = x1 x2 Ai (x1 x2 )i1 RT i=1

and show that A1 = 0.414, A2 = 0.080, A3 = 0.051, and A4 = 0.043. Problems related to Section 8.4 8.11 Loras et al. (1999) reported the following VLE data for the system of 3-methylpentane (1) and methyl 1,1-dimethylpropyl ether (2) at 101.3 kPa: x1 0.026 0.061 0.126 0.181 0.235 0.289 0.329 1 1.176 1.192 1.167 1.132 1.126 1.100 1.091 2 1.000 1.000 1.002 1.002 1.008 1.013 1.021 x1 0.370 0.432 0.488 0.508 0.565 0.620 0.674 1 1.082 1.063 1.053 1.050 1.039 1.029 1.022 2 1.026 1.036 1.042 1.041 1.052 1.063 1.085 x1 0.722 0.765 0.811 0.858 0.905 0.950 0.978 1 1.014 1.011 1.006 1.001 1.000 0.998 0.999 2 1.100 1.110 1.132 1.144 1.168 1.192 1.198

If the system is represented by the two-sux Margules equation, estimate the parameter A that minimizes the objective function !2 21 X Gex e A x1 x2 F = RT

i=1 i

(Answer: A = 0.183) 8.12 For the three-sux Margules equation, molar excess Gibbs energy is sometimes expressed as e Gex = x1 x2 (A21 x1 + A12 x2 ) (1) RT a) Compare Eq. (1) with Eq. (8.4-5) and conclude that A12 = A B b) Show that and A21 = A + B (2)

Note that when A12 = A21 , Eqs. (3) and (4) are equivalent to the two-sux Margules equations. 266

(3) (4)

8.13 A binary mixture of components 1 and 2 is represented by the three-sux Margules equation with temperature dependent parameters expressed in the form A = a1 + a2 T and B = b1 + b2 T (1)

a) Show that the innite-dilution activity coecients are expressed as ln = (a1 b1 ) + 1 ln = (a1 + b1 ) + 2 b) Show that the heat of mixing is given by h i e Hmix = x1 x2 (a2 + b2 ) x1 + (a2 b2 ) x2 R (4) a2 b2 T a2 + b2 T (2) (3)

c) For a mixture of mono-ethanol amine (1) and water (2), Kundu and Bandyopadhyay (2007) reported the following data: a1 = 1.531 a2 = 828.4 K b1 = 0.253 b2 = 13.84 K

Estimate and at 313 K. 1 2 (Answer: c) = 0.266 = 0.404) 1 2 8.14 For a binary mixture of di-isopropyl ether (1) and benzene (2), the following isothermal VLE data are reported by Villamanan et al. (2006) at 313.15 K: x1 0.0000 0.0504 0.1011 0.1498 0.1994 0.2497 0.2998 0.3500 0.3992 y1 0.0000 0.0878 0.1652 0.2318 0.2936 0.3515 0.4054 0.4563 0.5039 P ( kPa) 24.398 25.442 26.387 27.221 28.019 28.770 29.481 30.155 30.785 x1 0.3992 0.4489 0.4501 0.4991 0.5003 0.5490 0.5499 0.5986 0.6005 y1 0.5040 0.5503 0.5514 0.5954 0.5965 0.6391 0.6399 0.6814 0.6830 P ( kPa) 30.794 31.400 31.405 31.988 31.995 32.563 32.565 33.113 33.127 x1 0.6485 0.6991 0.7493 0.7978 0.8508 0.9078 0.9640 1.0000 y1 0.7231 0.7646 0.8052 0.8438 0.8854 0.9296 0.9727 1.0000 P ( kPa) 33.642 34.184 34.698 35.174 35.707 36.253 36.790 37.126

a) With the help of the following data e V1L = 145 cm3 / mol e V2L = 91 cm3 / mol

calculate the activity coecients using Eqs. (1) and (2) of Problem 8.10. b) If the activity coecients are represented by the three-sux Margules equation, plot e (Gex /RT )/x1 x2 versus x1 and show that the Margules parameters are given by A = 0.165 and B = 0.044 267

c) Show that the linearization of Eq. (8.4-6), i.e., a plot of ln 1 /x2 versus x2 , yields 2 A = 0.162 and B = 0.035

d) Show that the linearization of Eq. (8.4-7), i.e., a plot of ln 2 /x2 versus x1 , yields 1 A = 0.158 and B = 0.060

24 X P Pcalc 2 F = P i i=1

where

vap vap Pcalc = P1 x1 1 + P2 x2 2

By minimizing this objective function, they evaluated the parameters A and B as A = 0.171 and B = 0.060

Compare the predictions of activity coecients using the parameters obtained from four different approaches. 8.15 The molar excess Gibbs energy expression for the van Laar model, Eq. (8.4-12), is developed as follows: e e a) Assuming S ex = V ex = 0, show that b) By denition

e e Gex = U ex

(1)

e e U ex = Umix e U IGM

k X i=1

e xi Ui !

k X i=1

(2)

Note that the second term on the right-hand side of Eq. (3) is zero. For the van der Waals equation of state, Eqs. (6.1-32) and (3.6-14) give e e Umix U IGM = e e Ui UiIG = Amix RT amix = Zmix e V Ai RT ai = Zi e V +

i

e e = Umix U IGM +

k X i=1

e xi UiIG

e e xi Ui UiIG

(3)

(4)

mix

(5)

Substitute Eqs. (4) and (5) into Eq. (3) to obtain e e U ex = Gex =

amix e Vmix

k X xi ai i=1

268

e Vi

(6)

k k XX i=1 j=1 k X i=1 k X i=1

xi bi

(7)

e Gex = where

k X xi ai i=1

xi xj aij (8) xi bi

bi

aij =

aii ajj

(9)

k k XX i=1 j=1

xi xj

e Gex =

ai bj aij bi

k X i=1

(10)

xi bi

e) For a binary mixture show that Eq. (10) becomes e Gex = x1 x2 b1 b2 x1 b1 + x2 b2 2 a1 a2 b1 b2 2 a1 a2 b1 b2 (11)

2 a1 a2 b1 b2

b2 B= RT

(12)

and show that Eq. (11) reduces to e Gex = x1 x2 AB Ax1 + Bx2 (13)

8.16 When A = B, show that the van Laar and the two-sux Margules models become identical. 8.17 For a binary mixture of ethanol (1) and benzene (2) at 343 K, the van Laar parameters are A = 1.946 and B = 1.610. a) Calculate the activity coecients for a mixture containing 30 mol % ethanol. b) Calculate the activity coecients at innite dilution. c) Using the values of the activity coecients at innite dilution, determine the parameters of the three-sux Margules equation.

269

d) Use the Margules equation and calculate the activity coecients for a mixture containing 30 mol % ethanol. (Answer: a) 1 = 2.327, 2 = 1.206 b) = 7, = 5 c) A = 1.778, B = 0.168 1 2 d) 1 = 2.351, 2 = 1.206) 8.18 For a binary mixture of ethanol (1) and water (2), the following vapor-liquid equilibrium data have been reported by Pemberton and Mash (1978) at 303.15 K: P ( bar) 0.07329 0.08723 0.09303 0.09663 x1 0.10991 0.24688 0.38655 0.50492 y1 0.4743 0.5907 0.6404 0.6797 P ( bar) 0.09999 0.10341 0.10445 x1 0.63434 0.80840 0.92444 y1 0.7329 0.8337 0.9284

Evaluate the parameters of the van Laar activity coecient model graphically by plotting e x1 /(Gex /RT ) versus x1 /x2 .

8.19 If the activity coecients are represented by the Wilson equations, for an equimolar mixture show that h i 12 21 ln 1 = ln 0.5 (1 + 12 ) + (1) 1 + 21 1 + 12 h i 21 12 (2) ln = ln 0.5 (1 + 21 ) + 2 1 + 12 1 + 21 where and represent the activity coecients at x1 = x2 = 0.5. Add Eqs. (1) and (2) to 1 2 get 4 1 (3) 21 = 1 2 (1 + 12 )

Show that the substitution Eq. (3) into Eq. (1) leads to # " 1 (1 + 12 ) (1 + 12 ) 12 1 2 = 1 ln + 2 1 + 12 4

(4)

The value of 12 is obtained from the solution of this transcendental equation. Once 12 is determined, 21 can be evaluated from Eq. (3). 8.20 Prasad et al. (2007) reported the following vapor-liquid equilibrium data for a binary mixture of trichloroethylene (1) and p-cresol (2) at 95.23 kPa:

270

The vapor pressures of pure components are given by the Antoine equation as

vap ln P1 = 14.1654

3028.13 T 43.15

vap ln P2 = 14.1815

3479.39 T 111.30

where P is in kPa and T is in K. The densities of trichloroethylene and p-cresol are 1464 and 1154 kg/ m3 , respectively. a) Calculate the activity coecients as a function of composition. b) Use the equations given in Problem 8.19 to evaluate the Wilson parameters. Note that Prasad et al. (2007) evaluated the Wilson parameters as 12 11 = 103.56 K R and 21 22 = 630.97 K R

10 X P Pcalc 2 F = P i i=1

(Answer: b) (12 11 )/R = 77.1 K, (21 22 )/R = 590.4 K) 8.21 For a binary system of ethanol (1) and methyl butanoate (2) at 346.3 K, Constantinescu and Wichterle (2002) reported the following NRTL parameters: 12 = 0.356 21 = 0.460 = 1.0914

Estimate the innite dilution activity coecients. (Answer: = 2.678 = 3.053) 1 2 8.22 Note that the molar excess enthalpy can be calculated from Eq. (8.2-19), i.e., " !# e e H ex Gex = T2 R T RT

P,xj

(1)

a) For the NRTL model, let the parameters 12 and 21 be dependent on temperature in the form b12 b21 and 21 = a21 + (2) 12 = a12 + T T Show that the substitution of Eq. (8.4-26) into Eq. (1) leads to ) ( G21 b21 x1 (1 21 ) + G21 x2 G12 b12 x2 (1 12 ) + G12 x1 e H ex = x1 x2 + (3) R (x1 + G21 x2 )2 (x2 + G12 x1 )2 For a binary system of 2-methylamino ethanol (1) and water (2), Mundhwa and Henni (2007) reported the following parameters: 12 = 67.695 159.767 T 21 = 20.123 1265.64 T

where T is in K. If the nonrandomness parameter is = 0.019, calculate the molar excess enthalpy at 298.15 K as a function of composition and compare with the following experimental data:

271

For a binary system of formamide (1) and ethanol (2), Zarei and Iloukhani (2003) reported the following parameters: 12 11 = 2733.86 J/ mol e V1L = 44.87 cm3 / mol 21 22 = 1271.70 J/ mol e V2L = 58.35 cm3 / mol

b) For a binary system represented by the Wilson equation, show that the substitution of Eq. (8.4-18) into Eq. (1) leads to e ex = x1 x2 (12 11 )12 + (21 22 )21 (4) H x1 + 12 x2 x2 + 21 x1

Calculate the molar excess enthalpy at 298.15 K as a function of composition and compare with the following experimental data:

Problems related to Section 8.5 8.23 The activity coecient expressions for a regular mixture, Eqs. (8.5-2) and (8.5-3), are developed as follows: e e a) Assuming S ex = V ex = 0, follow the procedure outlined in Problem 8.14 and show that

k X e e e eex = U ex = Umix U IGM ei UiIG e xi U G i=1

(1)

b) In the van Laar model, the terms on the right-hand side of Eq. (1) are evaluated with the help of the van der Waals equation of state. The Scatchard-Hildebrand theory, on the other hand, introduces the concept of cohesive energy density, Cii . Cohesive energy density (in J/ cm3 ) is the change in internal energy of species i in going from the liquid to the ideal gas state, i.e., e e UiIG Ui Cii = (2) e VL

i

272

In other words, it is the energy required to vaporize a liquid per unit liquid volume. c) For the mixtures, extension of Eq. (2) is given by Cmix = where Cmix is dened by Cmix = in which Cij = e d) Since V ex = 0, conclude that e e UiIGM Umix

k k XX i=1 j=1

eL Vmix

(3)

i j Cij

(4)

p Cii Cjj

(5)

e) For a binary mixture, show that the substitution of Eqs. (2)-(6) into Eq. (1) leads to p e e e e e Gex = 2 C11 + 21 2 C11 C22 + 2 C22 x1 V1L + x2 V2L + x1 V1L C11 + x2 V2L C22 1 2 f ) The relationship between the volume and mole fractions is given by 1 = e x1 V1L 2 = e x2 V2L

(6)

(7)

e eL x1 V1L + x2 V2

e eL x1 V1L + x2 V2

(8)

g) The solubility parameter, i , is dened as the square root of the cohesive energy density, i.e., p (10) i = Cii so that Eq. (9) takes the form eex = x1 V1L + x2 V2L 1 2 ( 1 2 )2 e e G (11)

(9)

Use Eq. (11) in Eqs. (8.3-19) and (8.3-20) to obtain Eqs. (8.5-2) and (8.5-3). h) At temperatures well below the critical temperature, Eq. (2) can be expressed as Cii = e Hivap RT e ViL (12)

Using Eqs. (10) and (12), estimate the solubility parameter and compare it with the value given in Table 8.1. Enthalpy of vaporization of benzene at 298 K is 33.83 kJ/ mol. (Answer: h) 18.6( J/ cm3 )1/2 )

273

8.24 The solubility of solid biphenyl (2) in liquid pyridine (1) at 297.3 K is reported by Choi and McLaughlin (1983) as x2 = 0.3742. Using the following data, estimate the activity coecient of biphenyl in the liquid mixture. e V1L = 84.87 cm3 / mol (Answer: 2 = 1.013) 1 = 20.259 ( J/ cm3 )1/2 2 = 19.304 ( J/ cm3 )1/2

e e e 8.25 When V1L = V2L = V L , show that the activity coecient expressions for a regular mixture reduce to those for the two-sux Margules equations with A= e V L ( 1 2 )2 RT

Problems related to Section 8.6 8.26 For a binary mixture of ethanol (1) and methylcyclohexane (2), Russinyol et al. (2004) reported the following isobaric VLE data under atmospheric pressure:

a) Use the Lagrange three-point formula and show that the activity coecients at innite dilution are given as = 8.605 = 12.961 1 2 b) Calculate molar excess Gibbs energy as a function of composition, t the data to the following equation 5 X e Gex = x1 x2 Ai (x1 x2 )i1 RT

i=1

and show that A1 = 2.046, A2 = 0.184, A3 = 0.356, A4 = 0.018, and A5 = 0.023. 8.27 The activity coecient of species i in a mixture is dened by Eq. (8.3-5) as i = bL i (T, P, xi ) i (T, P )

L

(1)

274

a) Consider a binary system of species 1 and 2. If the fugacity coecients can be calculated by the Redlich-Kwong equation of state, show that ln 1 B1 L L = (Z 1) (Z1 1) + ln B2 2 ! A11 B1 + ln 1 + L L B1 Z2 B2 Z1 s ! A11 B1 A22 B2 2 (1 k12 ) ln 1 + (3) L B2 A22 B2 Z2

L Z1 B1

= lim i

xi 0

bL i (T, P, xi ) i (T, P )

L

(2)

ln 2

B2 L L = (Z 1) (Z2 1) + ln B1 1

b) For a binary system of benzene (1) and cyclohexane (2) at 310.9 K and 1.013 bar, the innite dilution activity coecient for benzene is reported as = 1.48 (Twu and Coon, 1 1995). Estimate the binary interaction parameter, k12 , using Eq. (3). c) Assuming k12 to be independent of temperature, estimate the innite dilution activity coecient for cyclohexane at 314.9 K and 1.013 bar. (Answer: b) 0.0268 c) = 1.60) 2 Problems related to Section 8.7 8.28 For a binary system, the molar excess Gibbs energy is given by e Gex = A x1 x2 2 RT (1)

ln 1 = A x2 (x2 x1 ) 2 ln 2 = 2 A x2 x2 1 b) Show that Eqs. (2) and (3) satisfy the Gibbs-Duhem equation, Eq. (8.8-4).

(2) (3)

8.29 Mirmehrabi et al. (2006) proposed the following equation to express the molar excess Gibbs energy of a binary system: e Gex = A(x1 x2 ) RT a) Show that h i ln 1 = A x x1 + (1 2)x (1) 2 1 1 275

b) Show that Eqs. (1) and (2) satisfy the Gibbs-Duhem equation, Eq. (8.7-4). 8.30 For a binary system of ethanol (1) and water (2) at 298.15 K, Hansen and Miller (1954) expressed the activity coecient of ethanol as a function of composition as ln 1 = (1 x2 ) 1.531 1.289 x1 0.207 e 11 x1 1 a) Show that the activity coecient of water is given by ( ) i 0.0188 h 1 (1 + 11 x1 ) e 11 x1 ln 2 = x2 2.1755 1.289 x1 0.207 e 11 x1 1 2 x1

h i ln 2 = A x x1 + (1 2)x 1 2 2

(2)

b) Calculate the innite dilution activity coecients. (Answer: b) = 3.758 = 2.381) 1 2 8.31 One of the tests used to verify the consistency of VLE data is the innite dilution test. For a binary system of components 1 and 2, start with Eq. (8.3-10) to obtain e ln 1 ln 2 Gex /RT = + x1 x2 x2 x1 e Gex /RT x1 x2 ! = ln 1 and e Gex /RT x1 x2 ! = ln 2 (1)

a) Show that

(2)

x1 =0

x1 =1

e b) In the innite dilution test, it is required to plot Gex /(RT x1 x2 ) versus x1 , ln 1 versus x1 , e and ln 2 versus x1 on the same graph. If the data are consistent, the values of Gex /(RT x1 x2 ) at x1 = 0 and x1 = 1 should approach ln 1 and ln 2 , respectively, as closely as possible. This obviously raises the question of how to quantify the closeness? In the literature it is suggested that consistent data should satisfy ! ! Gex /RT Gex /RT e e ln 1 ln 2 x1 x2 x1 x2 x1 =0 x1 =1 I1 = 100 < 30 and I2 = 100 < 30 ln 1 ln 2 (3) c) For a binary system of 2-butanol (1) and octane (2), Hiaki et al. (1998) calculated the following activity coecients from VLE data at 343.15 K: x1 0.0425 0.0868 0.1678 0.2263 0.2598 0.3061 0.3420 0.4130 0.4487 1 4.9534 3.8434 2.8271 2.3529 2.1642 1.9524 1.8159 1.6103 1.5232 2 1.0072 1.0295 1.0664 1.1175 1.1509 1.1987 1.2405 1.3411 1.3960 x1 0.4941 0.5314 0.5882 0.6140 0.6502 0.6613 0.6883 0.7384 0.7603 1 1.4304 1.3628 1.2779 1.2440 1.2017 1.1884 1.1655 1.1190 1.0988 2 1.4723 1.5459 1.6779 1.7423 1.8522 1.8992 1.9743 2.1756 2.2990 x1 0.7891 0.8228 0.8475 0.8674 0.8858 0.9397 0.9539 1 1.0821 1.0602 1.0482 1.0380 1.0270 1.0130 1.0105 2 2.4214 2.6276 2.7930 2.9680 3.1351 3.5843 3.7849

276

e Plot Gex /(RT x1 x2 ) versus x1 , ln 1 versus x1 , and ln 2 versus x1 on the same graph and calculate I1 and I2 . (Answer: c) I1 = 2.7 I2 = 13.3) 8.32 Kyyny et al. (2001) reported the following isothermal VLE data for a binary system of 2-butanol (1) and 2,4,4-trimethyl-1-pentene (2) at 360 K: x1 0.0511 0.0533 0.0587 0.0929 0.1288 0.1792 0.2322 0.2814 0.3330 1 3.69 3.63 3.42 3.15 2.76 2.39 2.07 1.87 1.69 2 1.01 1.01 1.01 1.02 1.03 1.06 1.10 1.14 1.19 x1 0.3905 0.4579 0.5150 0.5831 0.6454 0.7008 0.7529 0.7815 0.7875 1 1.54 1.41 1.31 1.23 1.17 1.11 1.09 1.06 1.06 2 1.25 1.34 1.43 1.56 1.69 1.85 2.00 2.13 2.20 x1 0.8235 0.8595 0.8877 0.9140 0.9322 0.9517 0.9675 0.9807 1 1.03 0.98 0.98 0.97 0.97 0.97 0.98 0.99 2 2.42 2.83 2.95 3.18 3.44 3.73 3.86 3.93

a) Fit the data to a fth-order polynomial and show that 1 = 1.4280 2.6508 x1 8.7773 x2 + 31.9029 x3 38.5755 x4 + 15.2042 x5 ln 1 1 1 1 2 b) Show that the experimental data are consistent. (Answer: b) A = 2.9 D = 4.4) Problem related to Section 8.9 8.33 The NRTL model for a multicomponent system is given by k k X X ji Gji xj rj Grj xr k X Gij xj j=1 r=1 ln i = k + ij k k P X X j=1 Gmj xm mi xm Gmj xm

m=1 m=1 m=1

where

gij gjj Gij = exp( ij ij ) ij = ji RT Merzougui et al. (2011) reported the following data for a ternary mixture of water (1), methanol (2), and dichloromethane (3) at 293.15 K: ij = ij 12 13 23 gij gjj ( cal/ mol) 238.5741 749.2058 359.8070 gji gii ( cal/ mol) 566.9698 1498.0961 1108.6181 ij 0.2 0.2 0.2

Calculate the activity coecients when x1 = 0.1, x2 = 0.3, and x3 = 0.6. (Answer: 1 = 2.170, 2 = 1.783, 3 = 2.794)

277

278

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